WO2018079634A1 - Liquid dispersion - Google Patents

Liquid dispersion Download PDF

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Publication number
WO2018079634A1
WO2018079634A1 PCT/JP2017/038601 JP2017038601W WO2018079634A1 WO 2018079634 A1 WO2018079634 A1 WO 2018079634A1 JP 2017038601 W JP2017038601 W JP 2017038601W WO 2018079634 A1 WO2018079634 A1 WO 2018079634A1
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Prior art keywords
compound
meth
acrylate
dispersion
weight
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PCT/JP2017/038601
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French (fr)
Japanese (ja)
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WO2018079634A8 (en
Inventor
能宜 岡田
中島　秀人
順次 森本
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住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201780066765.7A priority Critical patent/CN109843935B/en
Priority to KR1020197011158A priority patent/KR102412701B1/en
Publication of WO2018079634A1 publication Critical patent/WO2018079634A1/en
Publication of WO2018079634A8 publication Critical patent/WO2018079634A8/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D115/00—Coating compositions based on rubber derivatives
    • C09D115/02—Rubber derivatives containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

Definitions

  • the present invention relates to a dispersion.
  • Patent Document 1 describes an aqueous resin composition containing an acid-modified chlorinated polyolefin that can be used as an adhesive or a primer.
  • Patent Document 2 describes an aqueous emulsion excellent in adhesiveness, which contains a chlorinated rubber having a chlorine atom content of 45% by weight or more, a compound having one or more polymerizable groups, and water. Has been. However, such an aqueous emulsion does not always have sufficient adhesion when used after long-term storage.
  • the problem to be solved by the present invention is to provide a dispersion exhibiting excellent adhesiveness even when used after long-term storage.
  • a dispersion liquid containing water as a dispersion medium and containing a compound having a chlorinated rubber and a polymerizable group as a dispersoid The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water, 30 mL of the dispersion liquid is poured into a 100 mL container, and a measurement sample is prepared by stirring for 1 minute at a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer.
  • Back-scattered light by pouring into a sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting back-scattered light from the measurement sample at a position of 45 ° to the incident light
  • the intensity (%) measurement was started within 10 minutes from the preparation of the measurement sample, and the backscattering was measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell.
  • the maximum value ⁇ (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the light intensity (%) is expressed by the following formulas (I) to (III) ⁇ (upper part) ⁇ 20 (I) ⁇ (intermediate part) ⁇ 5 (II) ⁇ (bottom) ⁇ 10 (III) [Wherein, ⁇ (upper part) represents the maximum value ⁇ (%) at the upper part of the measurement sample, ⁇ (middle part) represents the maximum value ⁇ (%) at the intermediate part of the measurement sample, and ⁇ ( Bottom) shows the maximum value ⁇ (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion from the top. The part of the measurement sample divided by 1/3 is shown. ] A dispersion that meets the requirements of
  • the amount of the chlorinated rubber is 1 to 30 parts by weight relative to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 3 to 25 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 5 to 20 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount of the chlorinated rubber is 0.01 to 18% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the amount of the chlorinated rubber is 0.1 to 10% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the amount of the chlorinated rubber is 0.2 to 5% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described.
  • the amount of the compound having a polymerizable group and a cyclic structure is 1 to 60% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and a cyclic structure is 3 to 40% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and a cyclic structure is 5 to 20% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
  • the amount of the compound having a polymerizable group and having no cyclic structure is 0.4 to 50% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water.
  • the aforementioned [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 1 to 25% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water.
  • the dispersion liquid according to any one of [35].
  • the compound having a polymerizable group and having no cyclic structure is at least one selected from the group consisting of dodecyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate.
  • the dispersion liquid as described in any one of.
  • the compound having a polymerizable group and a cyclic structure is selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • the aforementioned [29], wherein the compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate.
  • any one of [1] to [41], wherein the compound having a polymerizable group is at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound.
  • the dispersion liquid described in 1. [49] The dispersion according to any one of [1] to [41], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.
  • [52] The dispersion according to any one of [1] to [51], further including a surfactant.
  • the dispersion of the present invention can adhere to an adherend with sufficient strength even when used after long-term storage.
  • the dispersion of the present invention contains water as a dispersion medium, and contains a chlorinated rubber and a compound having a polymerizable group as a dispersoid.
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
  • the dispersion (dispersion) of the present invention may be a suspension (suspension) in which the dispersoid is solid, or may be an emulsion (emulsion) in which the dispersoid is liquid, and some of the dispersoid is solid.
  • the remaining dispersoid may be a liquid dispersion.
  • the dispersion of the present invention is preferably an emulsion in which the dispersoid is a liquid, or a part of the dispersoid is a solid and the remaining dispersoid is a liquid, more preferably An emulsion in which the dispersoid is liquid.
  • the dispersion of the present invention it is preferable that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid.
  • that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid means that when the dispersion is filtered through a filter having a pore size of about 0.50 ⁇ m, at least a part of the chlorinated rubber is in the filtrate.
  • the chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
  • the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure, and all the compounds having a polymerizable group are at 23 ° C. and atmospheric pressure. More preferably, it is liquid.
  • at least a part of the chlorinated rubber has a polymerizable group that is liquid at 23 ° C. and atmospheric pressure (hereinafter sometimes abbreviated as “compound having a polymerizable group that is liquid”). It is preferable that the chlorinated rubber is dissolved in the solvent, and it is more preferable that the entire chlorinated rubber is dissolved in the compound having a polymerizable group that is liquid.
  • the fact that at least a part of chlorinated rubber is dissolved in a compound having a polymerizable group that is liquid means that a mixture of a chlorinated rubber and a compound having a polymerizable group that is liquid is filtered with a filter having a pore diameter of about 0.50 ⁇ m. It means that at least a part of the chlorinated rubber is contained in the filtrate when filtered.
  • the chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
  • the mixing temperature for preparing the mixture of the chlorinated rubber and the compound having a polymerizable group is usually 25 to 100 ° C., and the mixing time is preferably as short as possible.
  • the mixer used for this purpose include a Banbury mixer, a Henschel mixer, and a homomixer.
  • the total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight, preferably 3 to 30% by weight, more preferably 5% in the total of the chlorinated rubber, the compound having a polymerizable group and water. ⁇ 15 wt%. Adhesiveness will become favorable by making the total amount of the compound which has chlorinated rubber and a polymeric group into the said range.
  • the dispersion of the present invention was prepared by pouring 30 mL of the dispersion into a 100 mL container, and stirring for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer.
  • the measurement sample is poured into a cylindrical sample cell having a diameter of 25 mm, the measurement sample in the sample cell is irradiated with incident light having a wavelength of 880 nm, and backscattered light from the measurement sample is emitted at a position of 45 ° with respect to the incident light.
  • the measurement of the backscattered light intensity (%) by detection is started within 10 minutes from the preparation of the measurement sample, and the measurement is started at each of the top, middle and bottom of the measurement sample in the sample cell.
  • the maximum value ⁇ (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the backscattered light intensity (%) measured 30 minutes later is Formulas (I) to (III): ⁇ (upper part) ⁇ 20 (I) ⁇ (intermediate part) ⁇ 5 (II) ⁇ (bottom) ⁇ 10 (III) [Wherein, ⁇ (upper part) represents the maximum value ⁇ (%) at the upper part of the measurement sample, ⁇ (middle part) represents the maximum value ⁇ (%) at the intermediate part of the measurement sample, and ⁇ ( Bottom) shows the maximum value ⁇ (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion
  • the part of the measurement sample divided by 1/3 is shown.
  • One of the characteristics is to satisfy the above requirements.
  • the boundary between the upper part and the intermediate part of the measurement sample and the boundary between the intermediate part and the bottom part of the measurement sample are all included in the intermediate part of the measurement sample. Even if the dispersion liquid of the present invention satisfying such requirements is used after long-term storage, it can adhere to an adherend with sufficient strength.
  • a series of operations consisting of preparation of the measurement sample and measurement of the backscattered light intensity (%) is performed in an environment at 24-26 ° C. using an apparatus placed in an environment at 24-26 ° C.
  • preparation of the measurement sample that is, stirring of the dispersion liquid using a rotation / revolution stirrer
  • a dispersion liquid that is allowed to stand for 1 hour or more in an environment of 24 to 26 ° C. is used.
  • Examples of the rotation / revolution stirrer for preparing the measurement sample include “Rotation / revolution mixer: Awatori Nertaro ARE-310” manufactured by Sinky Corporation.
  • As an apparatus for measuring the amount of change in the backscattered light intensity (%) of the measurement sample for example, “turbiscan TOWER” manufactured by Formulation may be mentioned.
  • the “backscattered light intensity (%)” means “intensity of detected backscattered light with respect to the intensity of irradiated incident light (%)”. “The amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement” means “measurement It means a difference between the backscattered light intensity (%) measured 30 minutes after the start and the backscattered light intensity (%) measured 24 hours after the start of measurement.
  • the “maximum value in absolute value” means “a maximum value in a plurality of the absolute values calculated in each of the top, middle, and bottom of the measurement sample in the sample cell”.
  • the volume-based median diameter of the dispersoid in the dispersion is preferably 10 ⁇ m or less, more preferably 0.01 to 5 ⁇ m, still more preferably 0.01 to 2 ⁇ m, and still more preferably 0.01 ⁇ 1 ⁇ m. When the median diameter is within the above range, the standing stability of the dispersion is good.
  • the volume-based median diameter of the dispersoid means a particle diameter at which the integrated particle diameter distribution value is 50% on the volume basis. This median diameter can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA.
  • Chlorinated rubber means chlorinated natural rubber or synthetic rubber.
  • the chlorinated rubber may be one type or two or more types.
  • rubber means “uncrosslinked rubber” unless otherwise specified.
  • the chlorinated rubber used in the present invention may be a chlorinated rubber having a melting point or a chlorinated rubber having no melting point. It is preferable to use a chlorinated rubber having a melting point.
  • the melting point of the chlorinated rubber is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, further preferably 240 ° C. or higher, preferably 350 ° C. or lower, more preferably 300 ° C. or lower.
  • the melting point of the chlorinated rubber can be measured by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • An example of the DSC apparatus is DSC-60 Plus manufactured by Shimadzu Corporation.
  • the chlorine atom content of the chlorinated rubber is preferably 45% by weight or more, more preferably 45 to 85% by weight, still more preferably 55 to 80% by weight.
  • chlorinated rubber those having no carboxy group and carboxylic anhydride structure are preferably used.
  • the dispersion liquid of the present invention containing such a chlorinated rubber is used as an aqueous adhesive, primer or raw material thereof, the concern about the decrease in water resistance of the coating film is extremely small and effective.
  • the chlorinated rubber is not particularly limited as long as it is chlorinated natural rubber or synthetic rubber.
  • chlorinated natural rubber chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / chlorinated cyclic conjugate Diene adducts, chlorinated butadiene styrene copolymers, brominated poly (2,3-dichloro-1,3-butadiene) and ⁇ -haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymers Etc.
  • a chlorinated rubber synthesized from a raw material containing a monomer having 4 or more carbon atoms is preferred.
  • the chlorinated rubber is more preferably at least one selected from the group consisting of chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber, more preferably chlorinated natural rubber, chlorinated isoprene rubber or chlorinated butadiene. It is rubber.
  • a conventionally known method can be adopted. For example, a method in which natural rubber or synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene, and chlorine gas is blown; the natural rubber or synthetic rubber is suspended or emulsified in water Injecting chlorine gas with water; Introducing chlorine gas while irradiating ultraviolet rays with natural rubber or synthetic rubber suspended or emulsified in water; Contacting natural rubber or synthetic rubber with liquid chlorine under low pressure And chlorinating directly.
  • a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene
  • the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a wet state.
  • natural rubber when chlorinated, it can be chlorinated by blowing chlorine gas into latex natural rubber.
  • polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water and emulsified, and then uniformly chlorinated polyisoprene can be obtained by blowing chlorine gas.
  • the polystyrene-reduced weight average molecular weight (Mw) of the chlorinated rubber is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, particularly preferably 10,000 or more, preferably 400,000 or less, more preferably 200,000 or less.
  • Mw can be measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • chlorinated rubber for example, commercially available products and known methods or those manufactured according to the methods can be used.
  • Commercially available products include, for example, Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S -90, Pergut S-130, Pergut S-170 (Covestro), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK).
  • Supercron registered trademark
  • CR-10 CR-20
  • Pergut S-40 Pergut S -90
  • Pergut S-130 Pergut S-170
  • Alloprene registered trademark
  • R10, R20, R40 manufactured by ICI UK.
  • the method of patent 2660478 is mentioned, for example.
  • the amount of the chlorinated rubber is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, still more preferably 5 to 20 parts by weight based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part.
  • the amount of the chlorinated rubber is preferably 0.01 to 18% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. 2 to 5% by weight.
  • (meth) acryl means “acryl and methacryl”
  • (meth) acryloyl” means “acryloyl and methacryloyl”.
  • Other expressions of “(meta)” have the same meaning.
  • the compound having a polymerizable group is preferably at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound, and more preferably a compound having an ethylenically unsaturated bond.
  • the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is preferably 1 to 3, more preferably 1 to 2.
  • Examples of the compound having one ethylenically unsaturated bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam).
  • heterocyclic ethylenically unsaturated compounds for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam.
  • heterocyclic (meth) acrylates such as morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meta) Acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), alkyl (meth) acrylate (for example, methyl (meth) acrylate, eth
  • Examples of the compound having one ethylenically unsaturated bond and having a cyclic structure include (meth) acrylate having an alicyclic skeleton (for example, cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl)) Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonor Bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] dec-8-yl (Meta
  • Examples of the compound having two ethylenically unsaturated bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, polyoxyalkylene glycol di- (Meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Liethylene glycol-propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-
  • Examples of the compound having two ethylenically unsaturated bonds and having a cyclic structure include di (meth) acrylates (for example, 2,2) of adducts of alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) of bisphenol A.
  • bifunctional epoxy resin for example, 2,2-bis (glycidyl oxyphe Le) propane (meth) acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, etc.
  • Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocyanate Nurate, tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, tris (hydroxypropyl) Isocyanurate of tri (meth)
  • the number of carbon atoms of the compound having an ethylenically unsaturated bond is preferably 5 to 25, more preferably 6 to 23, and still more preferably 8 to 20.
  • epoxy compound examples include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1 , 2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl Ether, neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycol Diether, brominated bisphenol A diglycidyl ether, brominated
  • epoxy compound aromatic epoxides and alicyclic epoxides are preferable and alicyclic epoxides are more preferable from the viewpoint of excellent curing speed.
  • oxetane compound examples include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, 1,4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like.
  • the compound having a polymerizable group may be solid or liquid at 23 ° C. and atmospheric pressure, and is preferably liquid.
  • the amount of the compound having a polymerizable group in the dispersion of the present invention is preferably 70 to 99 parts by weight, more preferably 75 to 97 parts, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part by weight, more preferably 80 to 95 parts by weight.
  • the compound having a polymerizable group is preferably a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure.
  • the compound having a polymerizable group and having no cyclic structure is preferably 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1,6-hexane. It is at least one selected from the group consisting of diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate, and more preferably dodecyl (meth).
  • the compound having a polymerizable group and a cyclic structure is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • at least one selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate.
  • the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure
  • the compound has a polymerizable group and is cyclic
  • the amount of the compound having no structure is preferably 0.4 to 50% by weight, more preferably 1 to 25% by weight, and still more preferably 3% in the total of the chlorinated rubber, the compound having a polymerizable group and water.
  • the amount of the compound having a polymerizable group and a cyclic structure is preferably from 0.01 to 30% by weight, more preferably in the total of the chlorinated rubber, the compound having a polymerizable group and water. It is 0.1 to 15% by weight, more preferably 0.2 to 5% by weight.
  • the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure
  • the compound has a polymerizable group and is cyclic
  • the amount of the compound having no structure is preferably 40 to 99% by weight, more preferably 60 to 97% by weight, and still more preferably 80 to 95% by weight in the total of the compounds having a polymerizable group.
  • the amount of the compound having a polymerizable group and a cyclic structure is preferably 1 to 60% by weight, more preferably 3 to 40% by weight, and still more preferably in the total of the compound having a polymerizable group. Is from 5 to 20% by weight.
  • Water> There is no limitation in particular as water which the dispersion liquid of this invention contains, For example, tap water or deionized water is used.
  • the dispersion of the present invention may contain other components different from water, chlorinated rubber and the compound having a polymerizable group. Only 1 type may be used for another component and it may use 2 or more types together.
  • Other components include, for example, polymerization inhibitors, surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers.
  • Sensitizers other resins or rubbers different from chlorinated rubber, phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, preservatives, anti-settling agents , Antioxidant, heat stabilizer, thixotropic agent, thickener, antifoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent Transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate , Clay, kaolin, finely divided silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and fillers of inorganic or organic, such as Celite,
  • Polymerization inhibitor> There is no limitation in particular in a polymerization inhibitor, A well-known polymerization inhibitor can be used.
  • the polymerization inhibitor include hydroquinone, methylhydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p- Methylphenol, 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p- Examples include benzoquinone, 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, and phenothiazine.
  • Examples of commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Metoquinone Flakes, Nonflex Alba, MH, TBH, PBQ, tolquinone, TBQ (manufactured by Seiko Chemical Co., Ltd.) and the like can be mentioned.
  • the polymerization inhibitor has the effect of increasing the storage stability of the dispersion and ensuring curability.
  • the amount of the polymerization inhibitor in the dispersion is preferably 0.005 to 0.4 weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Parts, more preferably 0.01 to 0.4 parts by weight, even more preferably 0.01 to 0.3 parts by weight, still more preferably 0.02 to 0.3 parts by weight, still more preferably 0.02 to The amount is 0.2 parts by weight, particularly preferably 0.035 to 0.2 parts by weight.
  • the polymerization inhibitor a polymerization inhibitor that is soluble in a compound having a liquid polymerizable group is preferable.
  • the surfactant preferably acts as an emulsifier.
  • examples of the surfactant include a cationic, anionic, amphoteric or nonionic surfactant, and an anionic or nonionic surfactant is preferable.
  • Surfactants may be used alone or in combination of two or more.
  • anionic surfactant examples include fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, amino acid condensate of higher fatty acid such as sodium lauroyl sarcosine, sodium N-lauroyl glutamate, etc.
  • Higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, dodecylbenzene sulfone Acid aryl, alkylaryl sulfonates such as diisopropylnaphthalene sulfonate, formalin condensates of alkyl aryl sulfonate, pentadecane-2-sulfate Higher alcohol sulfates such as dipolyoxyethylene dodecyl ether phosphates, polyoxyethylene alkyl phosphates such as lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxy Ethy
  • Examples of the cationic surfactant include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salt, alkylisoquinolinium salt and dialkylmorpholinium salt, benzethonium chloride, And polyalkylvinylpyridinium salts, alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, Examples include allyltrialkylammonium salt, diallyldialkylammonium salt, and polydiallyldimethylammonium chloride.
  • alkylamine hydrochlorides such as dodecylamine hydrochloride
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid.
  • Ester polyoxypropylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxye Lenalkylamine, polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, Examples include polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol and the like.
  • amphoteric surfactants include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine, and lauryl dimethylamine oxide.
  • Examples of commercially available surfactants include EMAL 0, EMAL 10G, EMAL 2F paste, EMAL 20C, EMAL E-27C, EMAL 270J, EMAL E-27C, Neoperex GS, Neoperex G-15, Neoperex G -25, Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demol N, Demal EP, Emulgen 102KG, Emulgen 104P, Emulgen 105, Emalgen 106, Emulgen 108, Emulgen 404, Emulgen 130K, Emulgen 147, Emulgen LS-106, Emulgen LS-110, Emulgen A-60, Emulgen 109P, Emulgen 350, Latemul PD-420, Rheodor 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Amhitor 24B,
  • the dispersion of the present invention preferably contains a surfactant.
  • the amount thereof is preferably 1 part by weight or more, preferably 30 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Below, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.
  • the photopolymerization initiator is a compound that generates active species by the action of light.
  • Examples of the photopolymerization initiator include a photo radical generator that generates an active radical by the action of light, a photo acid generator that generates an acid by the action of light, and a photo base generator that generates a base by the action of light. It is done.
  • photo radical generator examples include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), and carboxylic acid esters. .
  • benzoin compound examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
  • benzophenone compound examples include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert -Butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.
  • alkylphenone compound examples include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl).
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • triazine compound examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (t
  • photo radical generators can be used.
  • examples of commercially available photoradical generators include Irgacure (registered trademark) 1173, 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Sequol (registered trademark).
  • Irgacure registered trademark 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%
  • Irgacure registered trademark 1700
  • Irgacure® 1800 bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%)
  • BASF Japan Ltd. BASF Japan Ltd.
  • photoacid generator examples include sulfonic acid derivatives, onium salts, dicarboxylic imides, and the like.
  • sulfonic acid derivatives examples include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonates, benzoinsulfonates, and sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol. , Pyrogallol trisulfonates, benzyl sulfonates.
  • onium salts include tetrafluoroborate (BF 4 ⁇ ), hexafluorophosphate (PF 6 ⁇ ), hexafluoroantimonate (SbF 6 ⁇ ), hexafluoroarsenate (AsF 6 ⁇ ), hexachloroantimonate ( SbCl 6 ⁇ ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), fluorosulfonic acid ion (FSO 3-), include toluenesulfonate ion, trinitrobenzene sulfonate anion, a sulfonium salt and iodonium salts having an anion such as trinitrotoluene sulf
  • sulfonium salt examples include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium.
  • iodonium salt examples include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- ( 2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n- Tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium
  • onium salts examples include aromatic diazonium salts such as p-methoxybenzenediazonium and hexafluoroantimonate.
  • onium salts include, for example, Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI -L110, SI-L147 (above, Sanshin Chemical Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (above, manufactured by ADEKA), Irgacure 261, Irgacure 250 (made by BASF), CI-2481, CI-2624, CI-2638, CI-2064 (above, Japan) Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100,
  • Diaryliodonium salts that can be produced by the method can also be used. These may be used alone or in combination of two or more.
  • dicarboxylic imides examples include N- (methylsulfonyloxy) naphthalene-1,8-dicarboximide, N- (tosyloxy) naphthalene-1,8-dicarboximide, N-[(trifluoromethyl) sulfonyl Oxy] naphthalene-1,8-dicarboximide, N- (camphorsulfonyloxy) naphthalene-1,8-dicarboximide, N- (phenylsulfonyloxy) succinimide, N- (tosyloxy) succinimide, N-[(tri Fluoromethyl) sulfonyloxy] succinimide, N- (camphorsulfonyloxy) succinimide, N-[(trifluoromethyl) sulfonyloxy] phthalimide, N-[(trifluoromethyl) sulfonyloxy] phthalimide, N-[(
  • photobase generators include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, Examples include sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, ⁇ -lactone ring derivative compounds, amine imide compounds, and phthalimide derivative compounds. These may be used alone or in combination of two or more.
  • the amount thereof is preferably from the viewpoint of stability, reactivity, and odor with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is 0.01 parts by weight or more, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • Light stabilizer examples include an ultraviolet absorber and a hindered amine light stabilizer.
  • a light stabilizer may be used independently and may be used in combination of 2 or more type.
  • ultraviolet absorbers examples include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, 2,4-dihydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5 ′) -Tert Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzo
  • hindered amine light stabilizer examples include ester group-containing piperidines (for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine. 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (for example, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2) , 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (for example, 4- (phenylcarbamoyloxy) -2,2,6 , 6-Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1 6-dicarbamate, etc.), and high molecular weight piperidine polycondensates (eg, dimethyl-1- (2-
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 15 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
  • UV curable oligomer examples include urethane acrylate oligomer, epoxy acrylate oligomer, and polyester acrylate oligomer.
  • the ultraviolet curable oligomers may be used alone or in combination.
  • a commercially available urethane acrylate oligomer can be used.
  • Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (manufactured by Sartomer), U-4HA and U-6HA (Shin Nakamura Chemical Co., Ltd.) AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G and DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.).
  • a commercially available epoxy acrylate oligomer can be used.
  • Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartomer).
  • polyester acrylate oligomer A commercially available polyester acrylate oligomer can be used.
  • polyester acrylate oligomers include CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304 (Cartomer). It is done.
  • These polyester acrylate oligomers may be used alone or in combination.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 20 parts by weight or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • optical brightener examples include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4 -Bis (2-benzoxazolyl) naphthalene, dialkylstilbene and the like.
  • fluorescent whitening agents include Kayahor 3BS Liq. Kayahor TAC Liq. Kyaphor HBC Liq. Kayalight B, Kyaphor AS 150, Kyaphor CR 200, Kyaphor JB Liq. Mikawhite ATN conc.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 1 part by weight or less.
  • Leveling agent> As a leveling agent, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (manufactured by Kyoeisha Chemical Industries), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by BYK Japan) KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Footgent 222F, footage 251, FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352
  • the amount thereof is preferably 1 part by weight or more, preferably 20 parts by weight or less, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 parts by weight or less, and further preferably 5 parts by weight or less.
  • ⁇ Basic compound> As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example.
  • the basic compound is preferably ammonia or an organic amine compound.
  • Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Of these, N, N-dimethylethanolamine is preferred.
  • metal hydroxide examples include lithium hydroxide, potassium hydroxide and sodium hydroxide.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 20 parts per 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.
  • the amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
  • Organic solvent examples include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Alcohols such as ethanol, n-propanol, isopropyl alcohol and n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3 -Glycols such as methyl-1-butanol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary rib Ether) and butyl cellosolves of carbitol, ethylene glycol monomethyl
  • the amount of the organic solvent in the dispersion of the present invention is preferably 0 to 100 parts by weight, more preferably 0, from the viewpoint of odor etc. with respect to the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. -50 parts by weight, more preferably 0-30 parts by weight, still more preferably 0-10 parts by weight. It is particularly preferred that the dispersion of the present invention does not contain an organic solvent.
  • Crosslinking agent By including a crosslinking agent, there exists a tendency which adhesiveness, the water resistance of a contact bonding layer, and the solvent resistance of a contact bonding layer improve more.
  • the crosslinking agent include epoxy compounds, polyisocyanate compounds (particularly aliphatic polyisocyanate compounds), oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, hydrazines. Compounds and the like. Among these, aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline compounds, hydrazide compounds, and hydrazine compounds are preferable. Among these, an aqueous one (water-soluble or water-dispersible) is more preferable. These crosslinking agents may be used alone or in combination.
  • polyisocyanate compound examples include hexamethylene diisocyanate (HDI), 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and oligomers or polymers thereof.
  • HDI hexamethylene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • oligomers or polymers thereof examples thereof include Sumidur (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10 made by Sumika Covestrourethane.
  • carbodiimide compound examples include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like.
  • hydrazide compounds include Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecandiohydrazide), IDH (isophthalic acid dihydrazide), SAH (salicylic acid hydrazide) and the like. It is done.
  • hydrazine compound examples include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 30 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • the photosensitizer can be appropriately selected according to the wavelength to be enhanced.
  • the effective excitation wavelength range of the photosensitizer is usually 450 nm or less, preferably 250 to 380 nm.
  • Examples of photosensitizers include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and isoacyl 4-dimethylaminobenzoate. Can be mentioned.
  • the amount is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
  • the dispersion of the present invention may contain another resin or rubber different from the chlorinated rubber as long as the effects of the present invention are not impaired. Any other resin or rubber may be used alone or in combination of two or more.
  • rubber means an elastomer having elasticity
  • resin means a thermoplastic resin or thermosetting resin that does not have elasticity.
  • Examples of other resins or rubbers include ethylene-vinyl ester copolymers, styrene-maleic acid copolymers, resins having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and modified products, (meth) acrylic Resin, polystyrene, polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-vinylidene chloride Polymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated resin having a structural unit derived from ⁇ -olefin having 2 to 20 carbon atoms, polyurea, acrylonitrile-butadiene -Styrene copolymer,
  • the ethylene-vinyl ester copolymer is a copolymer containing an ethylene unit and a vinyl ester unit.
  • the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of tertiary carboxylic acid having 8 to 10 carbon atoms and so-called vinyl versatate (for example, trade name: Veova (manufactured by Shell Chemical Co., Ltd.). Units derived from alkyl acid vinyl esters such as (registered trademark) 10).
  • the ethylene-vinyl ester copolymer may contain units derived from monomers copolymerizable with ethylene and vinyl esters, in addition to ethylene units and vinyl ester units.
  • this monomer include vinyl halides such as vinyl chloride, monomers having a small amount of functional groups such as amide groups, and (meth) acrylic acid esters.
  • an ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as “EVA”) is preferable.
  • the ethylene-vinyl acetate copolymer has different properties depending on the vinyl acetate content and the like, but various vinyl acetate contents and shapes (films, blocks, fibers, foams) can be used.
  • the ethylene-vinyl acetate copolymer may contain olefin units other than ethylene units. Examples of the ethylene-vinyl acetate copolymer containing other olefin units include ethylene-octene-vinyl acetate copolymer, ethylene-butene-vinyl acetate copolymer, and ethylene-propylene-vinyl acetate copolymer. It is done.
  • Examples of the ethylene-vinyl ester copolymer include VINNOL® E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, and H40. / 60, H30 / 48M (Wacker Chemie AG) and the like.
  • the ethylene-vinyl ester copolymer may be in the form of an emulsion.
  • Such an emulsion may be produced by emulsion polymerization of monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available product may be used.
  • Examples of the emulsion of the ethylene-vinyl ester copolymer include Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ, 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (above, (Manufactured by Kuraray Co., Ltd.), Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa Polymer) (stock) ), Denka EVA TEX (registered trademark) # 20, # 30, # 40
  • Examples of the styrene-maleic acid copolymer include ARASTOR 700, 703S (manufactured by Arakawa Chemical Industry Co., Ltd.), SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley '). s).
  • Examples of the styrene-maleic acid copolymer emulsion include VE-1122 (manufactured by Seiko PMC Co., Ltd.).
  • the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Further, it may be reduced in molecular weight or high molecular weight by peroxide or the like.
  • Examples of the ⁇ -olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and vinylcyclohexane. Of these, ethylene and propylene are preferred.
  • Examples of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear ⁇ -olefin homopolymers such as low density polyethylene, ultra high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene; ethylene-propylene copolymer, propylene-1 An ⁇ -olefin copolymer such as a butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-hexene copolymer; and an ⁇ having 2 to 20 carbon atoms -Copolymerizable with olefin and ⁇ -olefin And a copolymer with a
  • the copolymer of an ⁇ -olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the ⁇ -olefin may contain one type of unit derived from each, It may contain two or more types of units derived from.
  • Examples of monomers copolymerizable with an ⁇ -olefin having 2 to 20 carbon atoms include, for example, ⁇ , ⁇ -unsaturated carboxylic acids and their anhydrides, metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -Unsaturated carboxylic acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes, etc.), (meth) acrylonitrile, vinyl halides, amides and halogenated vinylidenes, etc. It is done. These may be used alone or in combination.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monoethyl maleate , Maleic acid half ester, maleic acid half amide, itaconic acid half ester, itaconic acid half amide, and the like.
  • acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
  • Examples of the metal salt of ⁇ , ⁇ -unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specifically, the sodium salt and magnesium salt of (meth) acrylic acid are mentioned.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples thereof include dimethyl maleate and esterified products of methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.
  • vinyl esters examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versatate. Of these, vinyl acetate is preferred.
  • Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.
  • cyclic olefin examples include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1 , 2-dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like.
  • vinyl aromatic compound examples include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and Examples include vinyl naphthalene.
  • polyene compounds include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. Can be mentioned. These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.
  • Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Examples include methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, and 2,3-dimethyl-1,3-decadiene.
  • Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro- Examples include 1,3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.
  • Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadiene, 3,3-dimethyl-1,4-hexadiene, and 5-ethyl.
  • Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene. It is done.
  • aromatic non-conjugated polyene compound examples include divinylbenzene and vinylisopropenylbenzene.
  • Examples of the copolymer having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms include an ethylene unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, Ionomers in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid copolymer are neutralized with metal, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate Copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-isobutyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene- Ethylene-unsaturated carboxylic acid ester such as n-butyl acrylate
  • modified products having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms include resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms such as ⁇ , ⁇ -unsaturated carboxylic acids, etc.
  • denaturation by is mentioned.
  • the modification rate with ⁇ , ⁇ -unsaturated carboxylic acids and the like is preferably 0.1 to 10% by weight with respect to 100% by weight of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms before modification, More preferably, it is 0.2 to 5% by weight, and still more preferably 0.2 to 4% by weight.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acids include ⁇ , ⁇ -unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), ⁇ , ⁇ -unsaturated carboxylic acid esters (methyl maleate, methyl itaconate) ), ⁇ , ⁇ -unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.).
  • ⁇ , ⁇ -unsaturated carboxylic acids maleic acid, itaconic acid, citraconic acid, etc.
  • ⁇ -unsaturated carboxylic acid esters methyl maleate, methyl itaconate
  • ⁇ , ⁇ -unsaturated carboxylic anhydrides maleic anhydride, itaconic anhydride, citraconic anhydride, etc.
  • a modified product of a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is obtained by melting the resin and then adding an ⁇ , ⁇ -unsaturated carboxylic acid or the like to the melt.
  • the resin can be prepared by, for example, a method of dissolving the resin in an organic solvent such as toluene or xylene and then adding an ⁇ , ⁇ -unsaturated carboxylic acid or the like to the solution to modify the resin.
  • the chlorination rate of the chlorinated resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is preferably 5 to 80% by weight with respect to 100% by weight of the copolymer before modification, More preferably, it is 40 to 75% by weight, and further preferably 55 to 70% by weight.
  • Chlorination of a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms is obtained by dissolving or dispersing the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms in an organic solvent. It can be performed by a method of blowing chlorine gas into the chamber.
  • Examples of the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and modified products thereof include, for example, Mersen (registered trademark) H-6410M, H-6051, H-6960, H-6820, and H-6822X ( Tosoh Corporation), EVAL (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.), Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX, 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Polytail (registered trademark) H (Mitsubishi Chemical Corporation
  • the resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion.
  • Such an emulsion may be produced by emulsifying a resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms and a modified product thereof, or a commercially available product may be used.
  • Examples of emulsions of resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms and modified products thereof include Arrow Base (registered trademark) SA-1200, SB-1200, SE-1200, SB-1010 (Unitika).
  • Examples of the resin having a structural unit derived from a chlorinated ⁇ -olefin having 2 to 20 carbon atoms include Eraslene (registered trademark) 401A, 303B (Showa Denko KK), Harden (registered trademark) CY-9122P, CY-9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16-LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE-515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (made in Japan) Chemicals Co., Ltd.), and the like.
  • the resin having a chlorinated ⁇ -olefin derived structural unit having 2 to 20 carbon atoms may be in the form of an emulsion.
  • Such an emulsion may be produced by emulsifying a chlorinated resin having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms, or a commercially available product may be used.
  • Examples of emulsions of resins having structural units derived from chlorinated ⁇ -olefins having 2 to 20 carbon atoms include, for example, HARDLEN® EW-5303, EH-801, EW-5504, EZ-1000 and EZ- 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T and E-415 (Nippon Paper Chemical Co., Ltd.).
  • the polyurethane may be foamed polyurethane or non-foamed polyurethane, but is preferably non-foamed polyurethane.
  • non-foamed polyurethanes water-soluble or water-dispersible polyurethanes are preferable.
  • a commercially available polyurethane can be used. Examples of commercially available polyurethanes include Nipponan (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.).
  • water-soluble or water-dispersible polyurethanes include, for example, Dispacol (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA- 8756 and KA-8766 (Sumitomo Covestrourethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP- 60LM and AP-80 (DIC Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Ucourt UWS-145 ( Sanyo Chemical Industries, Ltd.), Superflex (registered trademark) 107M, 110, 126, 130 150, 160, 210, 300, 361, 370, 410, 420,
  • Polyvinyl chloride is obtained by a method such as suspension polymerization or bulk polymerization of vinyl chloride.
  • the polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and soft polyvinyl chloride. Preferably, it is soft polyvinyl chloride.
  • the polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 (Kaneka Corporation), and the like.
  • Examples of the polyvinyl chloride emulsion include Vinibrand 701, 700, and 711 (Nisshin Chemical Industry Co., Ltd.).
  • Chlorinated polyvinyl chloride is obtained by chlorinating polyvinyl chloride by a chlorination method such as a gas phase or a liquid phase.
  • polyvinyl chloride include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and other monomers.
  • other monomers include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, and maleic acid ester.
  • Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).
  • Examples of the polyvinylidene chloride include SARAN X05253-16 (manufactured by Dow Chemical Co., Ltd.), Saran Wrap (registered trademark) resin (manufactured by Asahi Kasei Co., Ltd.), and the like.
  • Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay).
  • Examples of the vinyl chloride-vinylidene chloride copolymer include IXAN SGA-1 (manufactured by Solvay).
  • vinylidene chloride- (meth) acrylic acid ester copolymer examples include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay).
  • the chloroprene resin is a chloroprene homopolymer or a copolymer of chloroprene and other monomers.
  • the other monomer include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, itaconic acid, and the like.
  • the acid-modified chloroprene resin is obtained by graft copolymerizing the chloroprene resin with at least one selected from ⁇ , ⁇ -unsaturated carboxylic acids and anhydrides thereof.
  • ⁇ , ⁇ -unsaturated carboxylic acids and acid anhydrides thereof include those exemplified as modified products of resins having structural units derived from ⁇ -olefins having 2 to 20 carbon atoms.
  • chloroprene resin and the acid-modified chloroprene resin examples include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, Y- 31 (Tosoh Corp.), Shoprene (Registered Trademark) W, AF, WHV, WXJ, WB (Showa Denko Co., Ltd.), and Denka Chloroprene (Registered Trademark) A-30, A-70, A-90, A -91, M-130L, DCR-11 (Denka Co., Ltd.) and the like.
  • Examples of emulsions of chloroprene resin and acid-modified chloroprene resin include Skyprene (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590 (Tosoh Corporation), Shoprene (registered trademark) 115, 571, 572, 650, 671A, 750, SD78 and SD77S (Showa Denko), and Denkachloroprene (registered trademark) LA-50 and LC -501 (Denka Co., Ltd.).
  • brominated butyl rubber examples include JSR BROMOBUTYL 2255, 2244 (JSR), Exxon Bromobutyl 2255 (ExxonMobil Chemical).
  • modified rubber examples include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and examples of commercially available products include Expro 50 (Exxon).
  • styrene block copolymer examples include a block copolymer composed of a diene block and a styrene block.
  • SB styrene-butadiene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • styrene-butadiene-butylene-styrene copolymer examples include a block copolymer composed of a diene block and a styrene block.
  • SB styrene-butadiene block copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • Examples thereof include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutylene diblock copolymer (SIB).
  • a hydrogenated product is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.
  • the dispersion of the present invention may contain a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose as another resin.
  • a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose as another resin.
  • the dispersion of the present invention may contain a tackifying resin as another resin.
  • resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, and indene resins.
  • rosin polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and Rosins such as esterified products; terpene polymers such as terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins, etc .; petroleum having 5 carbon atoms Petroleum resins obtained by polymerizing fractions, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms and their hydrogenated resins; petroleum resins such as maleic acid-modified products and fumaric acid-modified products, chlorinated paraffins, etc. It is done.
  • terpene resins examples include YS Resin PX, PXN, YS Polyster, Mighty Ace, YS Resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanoru 803L, 901 (Arakawa Chemical Industries, Ltd.) ) And Tertac 80 (Nippon Terpene Chemical Co., Ltd.).
  • terpene resin emulsion include Tamorol E-200NT and E100 (Arakawa Chemical Industries, Ltd.).
  • chlorinated paraffin examples include Enpara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Corp.), etc. Is mentioned.
  • the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, based on the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Is 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less.
  • a thickener can be used to adjust the viscosity of the dispersion.
  • the thickener include Adecanol (registered trademark) UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH -541VF, UH-550, UH-752 and H-756VF (ADEKA), and SN thickeners 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A- 813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, and 4050 (San Nopco).
  • the dispersion of the present invention can be produced by a method as described in the examples below. Hereafter, the manufacturing method of the dispersion liquid of this invention is demonstrated in detail.
  • the preliminary dispersion method is not particularly limited, and can be performed using known means and apparatuses.
  • known devices include a homomixer.
  • the number of stirring is preferably 5,000 to 20,000 rpm, more preferably 8,000 to 20,000 rpm, and the stirring time is preferably 2 to 10 minutes, more preferably 3 ⁇ 10 minutes. It is preferred to start stirring with the mixture at room temperature.
  • the obtained preliminary dispersion is homogenized using a high-pressure homogenizer.
  • the pressure of the high-pressure homogenizer is preferably 40 to 1,000 bar, more preferably 40 to 800 bar. If the pressure is less than 40 bar, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the pressure exceeds 1,000 bar, fine dispersion of the dispersoid is not improved.
  • the number of homogenization treatments with a high-pressure homogenizer is preferably 2 to 10 times, more preferably 3 to 8 times. If the number of treatments is less than two, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the number of treatments exceeds 10, the fine dispersion of the dispersoid is not improved. It is preferable to start the homogenization process by a high-pressure homogenizer after cooling the preliminary dispersion obtained by the homomixer to room temperature.
  • Examples of the high-pressure homogenizer include “LAB1000”, “LAB2000”, “15MR”, “G-MODEL”, “R-MODEL” manufactured by SMT Co., Ltd., and the like.
  • a diluted dispersion may be produced by adding water to the dispersion of the invention produced as described above and stirring. Moreover, you may add the other component (for example, leveling agent) to the dispersion liquid of this invention manufactured as mentioned above, and stir, and may manufacture the dispersion liquid containing another component.
  • the other component for example, leveling agent
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
  • this invention provides the coating film formed from the said dispersion liquid, and the hardened
  • this invention provides the laminated body by which the 1st base material, the said hardened
  • the first substrate is preferably made of an olefin polymer or an ethylene-vinyl acetate copolymer.
  • the cured product may further exist between the adhesive layer and the second substrate.
  • Examples of the material of the adherend to which the dispersion liquid of the present invention is applied, or the adherend (including the first base material and the second base material) on which the coating film and the cured product of the present invention are laminated include wood.
  • Wood materials such as plywood, medium density fiberboard (MDF), particle board, fiber board; cellulose materials such as cotton cloth, cotton-containing fibers, linen, rayon; (1) homopolymers and copolymers of ethylene; Olefin-based polymers such as propylene homopolymer and copolymer, (2) styrene homopolymer and copolymer, (3) polycarbonate, (4) acrylonitrile-butadiene-styrene copolymer (ABS resin), (5) Poly (meth) acrylic resin, (6) Polyester, (7) Polyether, (8) Polyvinyl chloride, (9) Foamed or non-foamed polyurethane, (10) Foamed Is an unfoamed ethylene-vinyl acetate copoly
  • the adherend may be made of one kind of material or may be made of two or more kinds of materials.
  • the adherend may be a kneaded molded product of the plastic material and a filler such as talc, silica, activated carbon, or carbon fiber.
  • the dispersion liquid of the present invention includes adhesion between cellulosic material and plastic material, polyvinyl chloride, ethylene-vinyl acetate copolymer, cotton-containing fiber, polyamide resin, olefin polymer, polyurethane. , Rubber or cross-linked rubber, and synthetic leather can be suitably used for adhesion.
  • the shape of the adherend include a film, a sheet, and a block shape, and an adherend having a film or sheet shape is preferable.
  • olefin polymer examples include resins having a structural unit derived from an ⁇ -olefin having 2 to 20 carbon atoms described in ⁇ Other resin or rubber> and modified products. Moreover, as a plastic material, what was demonstrated by ⁇ other resin or rubber> is mentioned, for example.
  • Cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Examples of other natural fibers include wool, silk and hemp.
  • Examples of chemical fibers include synthetic fibers (for example, polyester fibers and polyamide fibers), semi-synthetic fibers (for example, cellulose fibers such as acetate, protein fibers such as promix), and regenerated fibers (for example, rayon, And cellulose fibers such as cupra and polynosic) and inorganic fibers (for example, carbon fibers and glass fibers).
  • Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.
  • polyamide-based resin examples include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11 and polyamide 12.
  • the shape of the polyamide resin may be any of a film, a block, a fiber, or a foam.
  • Examples of rubber or cross-linked rubber include thermoplastic rubbers; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber and other diene rubbers; butyl rubber, ethylene-propylene rubber And non-diene rubbers such as ethylene-propylene-diene rubber, silicone rubber and fluororubber; and cross-linked products thereof.
  • the rubber or the crosslinked rubber may be used alone or in combination of two or more.
  • reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization accelerators, vulcanizing agents, sulfur, etc. may be used in combination. Good.
  • Synthetic leather includes both synthetic leather and artificial leather in the narrow sense. That is, the synthetic leather may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric or the like, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber, Artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber and further applying the synthetic resin may be used.
  • these synthetic resins include polyurethane resins, polyamide resins, polyamino acid resins, and the like, and polyurethane resins are preferable.
  • the dispersion of the present invention can be used effectively for adhesion of adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes.
  • the dispersion liquid of the present invention is used for constituting materials (covers) such as a hood, an insole, and an outer bottom in footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes. It is suitable as an adhesive, a primer or a raw material thereof for adhering the body.
  • the surface of these adherends may be smooth or may have irregularities. Moreover, in order to improve adhesiveness, you may surface-treat to a to-be-adhered body. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation.
  • the manufacturing method of the laminated body of this invention mentioned above is demonstrated.
  • the dispersion is applied to the surface of the first substrate, optionally the second substrate.
  • Application may be performed by a known method.
  • Known methods include, for example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brushing and spatula coating.
  • the application and drying of the dispersion may be performed only once, or may be performed twice or more.
  • the application and drying methods may be combined with each other, or different methods may be combined.
  • the coating film After applying the dispersion liquid to the first substrate, the coating film may be dried or heat-treated, and then electromagnetic waves may be irradiated.
  • the heating temperature is, for example, about 30 to 150 ° C., preferably about 40 to 80 ° C.
  • the heating time is, for example, about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes.
  • the coating film may be allowed to stand (natural drying) before and after drying or heat treatment of the coating film. It is preferable to form a cured product of the coating film by irradiating the coating film formed from the dispersion with electromagnetic radiation (particularly, ultraviolet rays).
  • examples of the light source therefor include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser.
  • a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a low pressure mercury lamp are preferable.
  • the peak illuminance of electromagnetic radiation is preferably 5 to 2000 mW / cm 2 , more preferably 10 to 2000 mW / cm 2 .
  • Integrated irradiation dose is preferably 20 ⁇ 3000mJ / cm 2, more preferably 100 ⁇ 2500mJ / cm 2.
  • a surface treatment may be applied to the first substrate.
  • the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and anchor layer formation.
  • cured material obtained from it can be ensured by reducing the water
  • the thickness of the coated film after drying is preferably about 0.01 to 300 ⁇ m, more preferably about 0.01 to 200 ⁇ m, and still more preferably about 0.01 to 50 ⁇ m.
  • a liquid adhesive is applied to at least one of the first substrate and the second substrate to which the dispersion is applied, and is dried or heat-treated.
  • These application and drying or heat treatment may be performed only once on at least one of the first base material and the second base material, but both the application and heat drying of the adhesive may be performed on both of them.
  • the application method of the adhesive, the thickness of the coating film after drying, the method of drying or heat treatment, conditions such as temperature and time, etc. can be changed as appropriate. The same conditions as the dispersion application described above may be selected, or different conditions may be selected.
  • the same adhesive may be applied to the first substrate and the second substrate, or different adhesives may be applied. May be. In order to adhere the first substrate and the second substrate satisfactorily, it is preferable to use the same adhesive.
  • the adhesive may be the dispersion used above or a commercially available adhesive.
  • the thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the substrate, and the like.
  • the thickness of the adhesive layer is preferably about 0.01 to 300 ⁇ m, more preferably about 0.01 to 200 ⁇ m.
  • the adherend Prior to applying the liquid adhesive to the adherend (first substrate and / or second substrate), the adherend may be subjected to the surface treatment described above.
  • the method for bonding the first substrate and the second substrate to which the dispersion and / or the adhesive is applied is not particularly limited, and these may be bonded by mechanical operation or manually. During bonding, heat, pressure, or both may be applied. In the case of heating, it is necessary to set the heating within a temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, and the heating temperature is preferably about 120 ° C. or less, more preferably It is about 100 ° C. or lower. Heating can be performed using a normal hot air circulating oven, an infrared heater, a microwave oven, or the like.
  • the pressure is, for example, about 100 g / cm 2 or more and less than the pressure at which the shapes of the first base material and the second base material are deformed.
  • the time is, for example, about 1 second to 10 days.
  • the first base material and the second base material include those similar to the adherend described above.
  • the first substrate is preferably a substrate made of an olefin polymer or an ethylene-vinyl acetate copolymer.
  • the second base material is preferably a base material selected from the group consisting of polyvinyl chloride, synthetic leather, rubber, cotton-containing fibers, and polyolefin polymers.
  • the adhesive layer can be obtained, for example, by applying a liquid polyurethane adhesive, a liquid rubber adhesive, a liquid acrylic adhesive, or a liquid epoxy adhesive, and removing water, an organic solvent, or the like.
  • liquid polyurethane adhesive examples include the above-described water-soluble or water-dispersible polyurethane.
  • liquid rubber adhesives include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), and styrene-butadiene-styrene.
  • liquid adhesives containing rubber components such as block copolymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). Only 1 type may be used for a rubber component and it may use 2 or more types together.
  • an adhesion-imparting resin such as rosin resin, terpene resin, and petroleum resin may be added to the rubber adhesive.
  • liquid acrylic adhesive examples include a liquid containing a copolymer of an acrylic ester and / or methacrylic ester as an adhesive component, a functional group-containing monomer, and a monomer intended to improve cohesion.
  • An adhesive is mentioned.
  • An isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like may be added to the liquid acrylic adhesive.
  • acrylic esters examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Preferred examples include n-octyl acrylate and n-lauryl acrylate.
  • Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Preferred examples include n-octyl methacrylate and n-lauryl methacrylate.
  • Examples of the functional group-containing monomer copolymerizable with acrylic acid ester and / or methacrylic acid ester include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; acrylic Hydroxyethyl ester, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc.
  • acrylic acid or hydroxyalkyl ester of methacrylic acid acrylamide, methacrylamide, diacetone (meth) acrylamide, N-methylolacrylamide, N-methylol N-substituted or unsubstituted acrylamide such as methacrylamide, N-butoxymethylacrylamide, N-butoxymethacrylamide; acrylic acid such as glycidyl methacrylate and glycidyl methacrylate Or, preferred examples include glycidyl ester of methacrylic acid; acrylonitrile and the like.
  • liquid epoxy adhesive examples include a liquid adhesive containing an epoxy resin having one or more epoxy groups per molecule on average.
  • the epoxy resin include an epoxy resin obtained from bisphenol A and epichlorohydrin, a polyglycidyl ether obtained from bisphenol F and epichlorohydrin, or hydrogenated bisphenol A and epichlorohydrin.
  • oxazolidone-modified epoxy resins novolac type epoxy resins, polyfunctional phenol type epoxy resins, various halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, cycloaliphatic epoxy resins, and the like can also be used. . These epoxy resins may be used alone or in combination of two or more.
  • Liquid polyurethane adhesives, liquid rubber adhesives, liquid acrylic adhesives and liquid epoxy adhesives may be in the form of solutions, dispersions or emulsions, and hot melt adhesives used in the molten state An agent may be used.
  • the adhesive constituting the adhesive layer may contain another component (for example, resin) different from the above-described components.
  • resin for example, resin
  • the resin that the adhesive may contain include, for example, an olefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE),
  • PVC polyvinyl chloride
  • PS polystyrene
  • PVAc polyvinyl acetate
  • PTFE polytetrafluoroethylene
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • AS resin acrylonitrile-butadiene-styrene copolymer
  • modified products of the resin may be used alone or in combination of two or more.
  • examples of the resin that the adhesive may contain include a tackifier resin.
  • tackifying resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogens thereof.
  • examples thereof include additive resins, other petroleum-based resins, coumarone resins, indene resins, polyurethane resins, and the like.
  • the adhesive may contain examples, for example, surfactants, photopolymerization initiators, light stabilizers, ultraviolet curable oligomers, fluorescent brighteners, leveling agents, basic compounds, and organic compounds.
  • the chlorine atom content of the chlorinated rubber is a value measured by a flask combustion-ion chromatography method.
  • the median diameter (volume basis) of the dispersoids described in the following table is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.
  • a measurement sample is prepared from the dispersions produced in Examples and Comparative Examples described later, and the measurement is started within 10 minutes from the sample preparation, and the upper part of the measurement sample in the sample cell;
  • the amount of change in backscattered light intensity (%) measured 24 hours after the start of measurement, relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement at each of the intermediate part and the bottom part The maximum value ⁇ in absolute value was calculated and evaluated according to the following criteria. The results are shown in the table below. ⁇ : All the requirements of the above formulas (I) to (III) are satisfied. ⁇ : Does not satisfy any or all of the requirements of the above formulas (I) to (III).
  • Chlorinated rubber 1 Pergut S20 (Covestro, chlorine atom content: 64.5% or more, melting point: 250 ° C., weight average molecular weight (Mw) in terms of polystyrene: 75,000, carboxy group and carboxylic anhydride structure Chlorinated rubber that does not have) Compound 1 having polymerizable group: dodecyl methacrylate (containing 970 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.) Compound having a polymerizable group 2: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.) Compound having polymerizable group 3: 2-phenoxyethylene glycol methacrylate (containing 100 ppm of 4-methoxyphenol, Shin-Naka
  • Surfactant 1 (5 parts) was placed in ion-exchanged water (300 parts) and stirred at 60 ° C. to prepare an aqueous solution of surfactant 1 (hereinafter referred to as “solution 2”).
  • solution 2 was added to solution 1 and stirred to prepare a mixture. Subsequently, the obtained mixture was stirred at 16,000 rpm for 5 minutes at room temperature using TK Robotics (manufactured by PRIMIX Co., Ltd.) equipped with a homomixer MARKII to obtain a milky white emulsion. After cooling the dispersion to room temperature, homogenization was performed 4 times using a high-pressure homogenizer “LAB1000” manufactured by SMT Co., Ltd. at 800 bar, and the resulting emulsion was filtered through a 200 mesh nylon net. A dispersion E1 which is an emulsion was obtained. The obtained dispersion E1 had a nonvolatile content concentration of 25%.
  • Dispersion E6 was produced using a solution to which the amount of fluorescent whitening agent shown in Table 1 was added.
  • Dispersion E7 was produced without using a photopolymerization initiator.
  • aqueous adhesives F1 to F12 Any one of dispersions E1 to E12, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan), and ion-exchanged water in the amounts shown in Table 2 are mixed, stirred with a three-one motor, and mixed with milk. Water-based adhesives F1 to F12 as turbid liquids were obtained. In Examples 1 to 7 and Comparative Examples 1 to 5 and later, a dispersion that further contains a leveling agent and is suitable as an adhesive is referred to as an “aqueous adhesive”.
  • Example 8 Production of laminate 1>
  • the water-based adhesive F1 was allowed to stand at 50 ° C. for 7 days in a blowing constant temperature incubator, and then applied to a foam of ethylene-vinyl acetate copolymer (EVA) as a first substrate using a brush ( Weight per unit area of the coated film after drying: about 3 g / m 2 ), dried at 70 ° C. for 5 minutes, and irradiated with ultraviolet rays using a conveyor type UV irradiation device (Eye Graphics Co., Ltd., Eye Grandage ECS-4011GX).
  • EVA ethylene-vinyl acetate copolymer
  • the adhesive 1 was applied to a cotton canvas (Johoku Kogyo Co., Ltd.) as the second substrate using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), It was oven dried at 70 ° C. for 5 minutes to obtain a laminate of cotton canvas and adhesive layer.
  • Adhesive 1 is applied to the surface on the cured product side of the laminate of EVA and cured product obtained as described above, and the surface on the adhesive layer side of the laminate of cotton canvas and adhesive layer, respectively.
  • the film was applied using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), and oven-dried at 70 ° C. for 5 minutes. Thereafter, the adhesive layers of the obtained EVA, cured product and adhesive layer laminate and cotton canvas and adhesive layer laminate were bonded together, pressure-bonded by hand, and further pressed at 3 MPa at 20 MPa.
  • the laminated body 1 which is a laminated body of EVA (1st base material), hardened
  • Examples 9 to 14 and Comparative Examples 6 to 10 Production of Laminates 2 to 12> EVA (first substrate), cured product, adhesive layer, cotton canvas (second), except that the water-based adhesive F1 was changed to any one of the water-based adhesives F2 to F12. Laminated bodies 2 to 12 which are laminated bodies with the base material) were obtained.
  • ⁇ Test Example 1 Evaluation of initial adhesiveness> The laminate is allowed to stand at room temperature for 5 minutes after the production, and is then laminated using a tensile tester (manufactured by Shimadzu Corp., Autograph) under the conditions of a peeling rate of 50 mm / min, a peeling angle of 180 degrees, and room temperature. The peel strength between EVA (first substrate) and cotton canvas (second substrate) was measured, and the initial adhesion was evaluated according to the following criteria. The results are shown in Table 3. ⁇ : Peel strength is 45 N / inch or more ⁇ : Peel strength is less than 45 N / inch
  • Types of laminates produced in Examples 8 to 14 and Comparative Examples 6 to 10 results of evaluation of types of water-based adhesive used and the amount of change in backscattered light intensity; and results of evaluation of initial adhesiveness and final adhesiveness Is shown in Table 3 below.
  • the laminates 1 to 7 manufactured using the water-based adhesives F1 to F7 that satisfy the requirements for the amount of change in the backscattered light intensity of the present invention are the water-based adhesives that do not satisfy the requirements for the amount of change in the backscattered light intensity of the present invention.
  • the initial adhesiveness and final adhesiveness were good.
  • the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.

Abstract

The present invention provides a liquid dispersion that contains water as a dispersion medium, chlorinated rubber as a dispersed material, and a compound having a polymerizable group, wherein: the sum amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60 wt% of the sum of the chlorinated rubber, the compound having a polymerizable group, and the water; and a maximum value α (%) in the absolute value of the amount of change of a backscattered light intensity (%) measured 24 hours after the start of measurement relative to a backscattered light intensity (%) measured 30 minutes after the start of measurement, under measurement conditions set forth in the description, meets the requirements (I) α (top) < 20, (II) α (middle) < 5, and (III) α (bottom) < 10 (where the meanings of terms such as α (top), α (middle), and α (bottom) are as set forth in the description).

Description

分散液Dispersion
　本発明は、分散液に関する。 The present invention relates to a dispersion.
　乳濁液および懸濁液のような分散液（特に水性分散液）は、接着剤等の様々な分野で多用されている。例えば、特許文献１には、接着剤またはプライマーとして利用することができる、酸変性塩素化ポリオレフィンを含む水性樹脂組成物が記載されている。しかし、このような水性樹脂組成物は、被着体に対して充分な強度で接着しないか、または被着体同士を充分な強度で接着することができなかった。また、特許文献２には、塩素原子含有量が４５重量％以上である塩素化ゴムと、１種以上の重合性基を有する化合物と、水とを含む、接着性に優れた水性エマルションが記載されている。しかし、このような水性エマルションは、長期保存後に使用した場合、接着性が必ずしも充分ではなかった。 Dispersions (especially aqueous dispersions) such as emulsions and suspensions are widely used in various fields such as adhesives. For example, Patent Document 1 describes an aqueous resin composition containing an acid-modified chlorinated polyolefin that can be used as an adhesive or a primer. However, such an aqueous resin composition does not adhere to adherends with sufficient strength, or adherends cannot adhere to each other with sufficient strength. Patent Document 2 describes an aqueous emulsion excellent in adhesiveness, which contains a chlorinated rubber having a chlorine atom content of 45% by weight or more, a compound having one or more polymerizable groups, and water. Has been. However, such an aqueous emulsion does not always have sufficient adhesion when used after long-term storage.
特開２００７－３１４７３号公報JP 2007-31473 A 国際公開第２０１５／１９４６１１号International Publication No. 2015/194611
　本発明が解決しようとする課題は、長期保存後に使用しても、優れた接着性を示す分散液を提供することにある。 The problem to be solved by the present invention is to provide a dispersion exhibiting excellent adhesiveness even when used after long-term storage.
　［１］　分散媒として水を含み、分散質として塩素化ゴムおよび重合性基を有する化合物を含む分散液であって、
　塩素化ゴムおよび重合性基を有する化合物の合計量が、塩素化ゴム、重合性基を有する化合物および水の合計中に１～６０重量％であり、
　３０ｍＬの分散液を１００ｍＬ容器に注ぎ、自転公転撹拌機を用いて、自転速度８００ｒｐｍおよび公転速度２，０００ｒｐｍの条件で１分間撹拌して測定試料を調製し、２０ｍＬの測定試料を直径２５ｍｍのシリンダー状の試料セルに注ぎ、試料セル中の測定試料に波長が８８０ｎｍである入射光を照射し、入射光に対して４５°の位置で測定試料からの後方散乱光を検出することによる後方散乱光強度（％）の測定を、測定試料の調製から１０分以内に開始し、試料セル中の測定試料の上部、中間部および底部のそれぞれにおける、測定を開始してから３０分後に測定した後方散乱光強度（％）に対する、測定を開始してから２４時間後に測定した後方散乱光強度（％）の変化量の絶対値における最大値α（％）が、下記式（I）～（III）：
α（上部）　＜２０　　　（I）
α（中間部）＜５　　　　（II）
α（底部）　＜１０　　　（III）
［式中、α（上部）は、測定試料の上部における前記最大値α（％）を示し、α（中間部）は、測定試料の中間部における前記最大値α（％）を示し、α（底部）は、測定試料の底部における前記最大値α（％）を示し、測定試料の上部、中間部および底部は、それぞれ、メニスカスの部分を除いた試料セル中の測定試料の高さを上から１／３ずつ分割した測定試料の部分を示す。］
の要件を満たす分散液。 [1] A dispersion liquid containing water as a dispersion medium and containing a compound having a chlorinated rubber and a polymerizable group as a dispersoid,
The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water,
30 mL of the dispersion liquid is poured into a 100 mL container, and a measurement sample is prepared by stirring for 1 minute at a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer. Back-scattered light by pouring into a sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting back-scattered light from the measurement sample at a position of 45 ° to the incident light The intensity (%) measurement was started within 10 minutes from the preparation of the measurement sample, and the backscattering was measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell. The maximum value α (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the light intensity (%) is expressed by the following formulas (I) to (III)
α (upper part) <20 (I)
α (intermediate part) <5 (II)
α (bottom) <10 (III)
[Wherein, α (upper part) represents the maximum value α (%) at the upper part of the measurement sample, α (middle part) represents the maximum value α (%) at the intermediate part of the measurement sample, and α ( Bottom) shows the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion from the top. The part of the measurement sample divided by 1/3 is shown. ]
A dispersion that meets the requirements of
　［２］　塩素化ゴムおよび重合性基を有する化合物の合計量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、３～３０重量％である前記［１］に記載の分散液。
　［３］　塩素化ゴムおよび重合性基を有する化合物の合計量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、５～１５重量％である前記［１］に記載の分散液。 [2] The dispersion according to [1], wherein the total amount of the chlorinated rubber and the compound having a polymerizable group is 3 to 30% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water. liquid.
[3] The dispersion according to [1], wherein the total amount of the chlorinated rubber and the compound having a polymerizable group is 5 to 15% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water. liquid.
　［４］　塩素化ゴム中の塩素原子含有量が、４５重量％以上である前記［１］～［３］のいずれか一つに記載の分散液。
　［５］　塩素化ゴム中の塩素原子含有量が、４５～８５重量％である前記［１］～［３］のいずれか一つに記載の分散液。
　［６］　塩素化ゴム中の塩素原子含有量が、５５～８０重量％である前記［１］～［３］のいずれか一つに記載の分散液。 [4] The dispersion according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 45% by weight or more.
[5] The dispersion according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 45 to 85% by weight.
[6] The dispersion according to any one of [1] to [3], wherein the chlorine atom content in the chlorinated rubber is 55 to 80% by weight.
　［７］　塩素化ゴムが、融点を有する塩素化ゴムである前記［１］～［６］のいずれか一つに記載の分散液。
　［８］　塩素化ゴムの融点が、１００℃以上である前記［７］に記載の分散液。
　［９］　塩素化ゴムの融点が、２００℃以上である前記［７］に記載の分散液。
　［１０］　塩素化ゴムの融点が、２４０℃以上である前記［７］に記載の分散液。 [7] The dispersion according to any one of [1] to [6], wherein the chlorinated rubber is a chlorinated rubber having a melting point.
[8] The dispersion according to [7], wherein the chlorinated rubber has a melting point of 100 ° C or higher.
[9] The dispersion according to [7], wherein the chlorinated rubber has a melting point of 200 ° C or higher.
[10] The dispersion according to [7], wherein the chlorinated rubber has a melting point of 240 ° C or higher.
　［１１］　塩素化ゴムの融点が、３５０℃以下である前記［７］～［１０］のいずれか一つに記載の分散液。
　［１２］　塩素化ゴムの融点が、３００℃以下である前記［７］～［１０］のいずれか一つに記載の分散液。 [11] The dispersion according to any one of [7] to [10], wherein the chlorinated rubber has a melting point of 350 ° C. or lower.
[12] The dispersion according to any one of [7] to [10], wherein the chlorinated rubber has a melting point of 300 ° C. or lower.
　［１３］　塩素化ゴムのポリスチレン換算の重量平均分子量が、１，０００以上である前記［１］～［１２］のいずれか一つに記載の分散液。
　［１４］　塩素化ゴムのポリスチレン換算の重量平均分子量が、３，０００以上である前記［１］～［１２］のいずれか一つに記載の分散液。
　［１５］　塩素化ゴムのポリスチレン換算の重量平均分子量が、５，０００以上である前記［１］～［１２］のいずれか一つに記載の分散液。
　［１６］　塩素化ゴムのポリスチレン換算の重量平均分子量が、１０，０００以上である前記［１］～［１２］のいずれか一つに記載の分散液。 [13] The dispersion according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 1,000 or more.
[14] The dispersion according to any one of [1] to [12], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 3,000 or more.
[15] The dispersion according to any one of [1] to [12], wherein the polystyrene equivalent weight average molecular weight of the chlorinated rubber is 5,000 or more.
[16] The dispersion according to any one of [1] to [12], wherein the weight average molecular weight in terms of polystyrene of the chlorinated rubber is 10,000 or more.
　［１７］　塩素化ゴムのポリスチレン換算の重量平均分子量が、４００，０００以下である前記［１］～［１６］のいずれか一つに記載の分散液。
　［１８］　塩素化ゴムのポリスチレン換算の重量平均分子量が、２００，０００以下である前記［１］～［１６］のいずれか一つに記載の分散液。 [17] The dispersion according to any one of [1] to [16], wherein the chlorinated rubber has a weight average molecular weight in terms of polystyrene of 400,000 or less.
[18] The dispersion according to any one of [1] to [16], wherein the chlorinated rubber has a polystyrene equivalent weight average molecular weight of 200,000 or less.
　［１９］　塩素化ゴムの量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１～３０重量部である前記［１］～［１８］のいずれか一つに記載の分散液。
　［２０］　塩素化ゴムの量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、３～２５重量部である前記［１］～［１８］のいずれか一つに記載の分散液。
　［２１］　塩素化ゴムの量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、５～２０重量部である前記［１］～［１８］のいずれか一つに記載の分散液。 [19] In any one of the above [1] to [18], the amount of the chlorinated rubber is 1 to 30 parts by weight relative to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. The dispersion described.
[20] In any one of the above [1] to [18], the amount of the chlorinated rubber is 3 to 25 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. The dispersion described.
[21] In any one of the above [1] to [18], the amount of the chlorinated rubber is 5 to 20 parts by weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. The dispersion described.
　［２２］　塩素化ゴムの量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．０１～１８重量％である前記［１］～［２１］のいずれか一つに記載の分散液。
　［２３］　塩素化ゴムの量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．１～１０重量％である前記［１］～［２１］のいずれか一つに記載の分散液。
　［２４］　塩素化ゴムの量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．２～５重量％である前記［１］～［２１］のいずれか一つに記載の分散液。 [22] In any one of the above [1] to [21], the amount of the chlorinated rubber is 0.01 to 18% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described.
[23] In any one of the above [1] to [21], the amount of the chlorinated rubber is 0.1 to 10% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described.
[24] In any one of the above [1] to [21], the amount of the chlorinated rubber is 0.2 to 5% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion described.
　［２５］　塩素化ゴムの少なくとも一部が、液状の分散質中に溶解している前記［１］～［２４］のいずれか一つに記載の分散液。
　［２６］　重合性基を有する化合物の少なくとも一部が、２３℃および大気圧下にて液状である前記［１］～［２５］のいずれか一つに記載の分散液。
　［２７］　塩素化ゴムの少なくとも一部が、２３℃および大気圧下にて液状である重合性基を有する化合物中に溶解している前記［２６］に記載の分散液。
　［２８］　分散質が、液状である前記［１］～［２７］のいずれか一つに記載の分散液。 [25] The dispersion according to any one of [1] to [24], wherein at least a part of the chlorinated rubber is dissolved in a liquid dispersoid.
[26] The dispersion according to any one of [1] to [25], wherein at least a part of the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure.
[27] The dispersion according to [26], wherein at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group that is liquid at 23 ° C. and atmospheric pressure.
[28] The dispersion according to any one of [1] to [27], wherein the dispersoid is a liquid.
　［２９］　重合性基を有する化合物が、重合性基を有し、且つ環状構造を有さない化合物と、重合性基および環状構造を有する化合物との混合物である前記［１］～［２８］のいずれか一つに記載の分散液。 [29] The above [1] to [28], wherein the compound having a polymerizable group is a mixture of a compound having a polymerizable group and having no cyclic structure and a compound having a polymerizable group and a cyclic structure The dispersion liquid as described in any one of these.
　［３０］　重合性基を有し、且つ環状構造を有さない化合物の量が、重合性基を有する化合物の合計中に、４０～９９重量％である前記［２９］に記載の分散液。
　［３１］　重合性基を有し、且つ環状構造を有さない化合物の量が、重合性基を有する化合物の合計中に、６０～９７重量％である前記［２９］に記載の分散液。
　［３２］　重合性基を有し、且つ環状構造を有さない化合物の量が、重合性基を有する化合物の合計中に、８０～９５重量％である前記［２９］に記載の分散液。 [30] The dispersion according to [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 40 to 99% by weight in the total of the compound having a polymerizable group.
[31] The dispersion according to [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 60 to 97% by weight in the total of the compound having a polymerizable group.
[32] The dispersion according to [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 80 to 95% by weight in the total of the compounds having a polymerizable group.
　［３３］　重合性基および環状構造を有する化合物の量が、重合性基を有する化合物の合計中に、１～６０重量％である前記［２９］～［３２］のいずれか一つに記載の分散液。
　［３４］　重合性基および環状構造を有する化合物の量が、重合性基を有する化合物の合計中に、３～４０重量％である前記［２９］～［３２］のいずれか一つに記載の分散液。
　［３５］　重合性基および環状構造を有する化合物の量が、重合性基を有する化合物の合計中に、５～２０重量％である前記［２９］～［３２］のいずれか一つに記載の分散液。　 [33] The amount of the compound having a polymerizable group and a cyclic structure is 1 to 60% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
[34] The amount of the compound having a polymerizable group and a cyclic structure is 3 to 40% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
[35] The amount of the compound having a polymerizable group and a cyclic structure is 5 to 20% by weight in the total of the compound having a polymerizable group, according to any one of the above [29] to [32] Dispersion.
　［３６］　重合性基を有し、且つ環状構造を有さない化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．４～５０重量％である前記［２９］～［３５］のいずれか一つに記載の分散液。
　［３７］　重合性基を有し、且つ環状構造を有さない化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、１～２５重量％である前記［２９］～［３５］のいずれか一つに記載の分散液。
　［３８］　重合性基を有し、且つ環状構造を有さない化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、３～２５重量％である前記［２９］～［３５］のいずれか一つに記載の分散液。 [36] The amount of the compound having a polymerizable group and having no cyclic structure is 0.4 to 50% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group, and water. The dispersion according to any one of [29] to [35].
[37] The aforementioned [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 1 to 25% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. The dispersion liquid according to any one of [35].
[38] The above [29], wherein the amount of the compound having a polymerizable group and having no cyclic structure is 3 to 25% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. The dispersion liquid according to any one of [35].
　［３９］　重合性基および環状構造を有する化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．０１～３０重量％である前記［２９］～［３８］のいずれか一つに記載の分散液。
　［４０］　重合性基および環状構造を有する化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．１～１５重量％である前記［２９］～［３８］のいずれか一つに記載の分散液。
　［４１］　重合性基および環状構造を有する化合物の量が、塩素化ゴム、重合性基を有する化合物および水の合計中に、０．２～５重量％である前記［２９］～［３８］のいずれか一つに記載の分散液。 [39] The above [29] to [38], wherein the amount of the polymerizable group and the compound having a cyclic structure is 0.01 to 30% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. The dispersion liquid as described in any one of these.
[40] The above [29] to [38], wherein the amount of the polymerizable group and the compound having a cyclic structure is 0.1 to 15% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. The dispersion liquid as described in any one of these.
[41] The above [29] to [38], wherein the amount of the polymerizable group and the compound having a cyclic structure is 0.2 to 5% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water. The dispersion liquid as described in any one of these.
　［４２］　重合性基を有し、且つ環状構造を有さない化合物が、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、１，６－ヘキサンジオール　ジ（メタ）アクリレート、１，９－ノナンジオール　ジ（メタ）アクリレート、および１，１０－デカンジオール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４１］のいずれか一つに記載の分散液。
　［４３］　重合性基を有し、且つ環状構造を有さない化合物が、ドデシル（メタ）アクリレート、および１，６－ヘキサンジオール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４１］のいずれか一つに記載の分散液。
　［４４］　重合性基を有し、且つ環状構造を有さない化合物が、ドデシルメタクリレート、および１，６－ヘキサンジオール　ジメタクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４１］のいずれか一つに記載の分散液。 [42] Compounds having a polymerizable group and having no cyclic structure are 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1,6- [29]-[41] which is at least one selected from the group consisting of hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate. ] The dispersion liquid as described in any one of.
[43] The compound having a polymerizable group and having no cyclic structure is at least one selected from the group consisting of dodecyl (meth) acrylate and 1,6-hexanediol di (meth) acrylate. [29] The dispersion according to any one of [41].
[44] The above [29] to [41], wherein the compound having a polymerizable group and having no cyclic structure is at least one selected from the group consisting of dodecyl methacrylate and 1,6-hexanediol dimethacrylate. ] The dispersion liquid as described in any one of.
　［４５］　重合性基および環状構造を有する化合物が、２－フェノキシエチレングリコール　（メタ）アクリレート、２－フェノキシジエチレングリコール　（メタ）アクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４４］のいずれか一つに記載の分散液。
　［４６］　重合性基および環状構造を有する化合物が、２－フェノキシエチレングリコール　（メタ）アクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４４］のいずれか一つに記載の分散液。
　［４７］　重合性基および環状構造を有する化合物が、２－フェノキシエチレングリコール　メタクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである前記［２９］～［４４］のいずれか一つに記載の分散液。 [45] The compound having a polymerizable group and a cyclic structure is selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. The dispersion according to any one of [29] to [44], which is at least one.
[46] The aforementioned [29], wherein the compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate. The dispersion according to any one of [44].
[47] The above [29] to [44], wherein the compound having a polymerizable group and a cyclic structure is at least one selected from the group consisting of 2-phenoxyethylene glycol methacrylate and tricyclodecane dimethanol di (meth) acrylate. ] The dispersion liquid as described in any one of.
　［４８］　重合性基を有する化合物が、エチレン性不飽和結合を有する化合物、エポキシ化合物、およびオキセタン化合物からなる群から選ばれる少なくとも一つである前記［１］～［４１］のいずれか一つに記載の分散液。
　［４９］　重合性基を有する化合物が、エチレン性不飽和結合を有する化合物である前記［１］～［４１］のいずれか一つに記載の分散液。 [48] Any one of [1] to [41], wherein the compound having a polymerizable group is at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound. The dispersion liquid described in 1.
[49] The dispersion according to any one of [1] to [41], wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.
　［５０］　エチレン性不飽和結合を有する化合物中のエチレン性不飽和結合の数が、１～３である前記［４８］または［４９］に記載の分散液。
　［５１］　エチレン性不飽和結合を有する化合物中のエチレン性不飽和結合の数が、１～２である前記［４８］または［４９］に記載の分散液。 [50] The dispersion according to [48] or [49], wherein the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is 1 to 3.
[51] The dispersion according to [48] or [49], wherein the number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is 1 to 2.
　［５２］　さらに界面活性剤を含む前記［１］～［５１］のいずれか一つに記載の分散液。
　［５３］　界面活性剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１重量部以上である前記［５２］に記載の分散液。
　［５４］　界面活性剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、３０重量部以下である前記［５２］または［５３］に記載の分散液。
　［５５］　界面活性剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１５重量部以下である前記［５２］または［５３］に記載の分散液。
　［５６］　界面活性剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１０重量部以下である前記［５２］または［５３］に記載の分散液。 [52] The dispersion according to any one of [1] to [51], further including a surfactant.
[53] The dispersion according to [52], in which the amount of the surfactant is 1 part by weight or more with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.
[54] The dispersion according to [52] or [53], wherein the amount of the surfactant is 30 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[55] The dispersion according to [52] or [53], wherein the amount of the surfactant is 15 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[56] The dispersion according to [52] or [53], wherein the amount of the surfactant is 10 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
　［５７］　さらに光重合開始剤を含む前記［１］～［５６］のいずれか一つに記載の分散液。
　［５８］　光重合開始剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、０．０１重量部以上である前記［５７］に記載の分散液。
　［５９］　光重合開始剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、４０重量部以下である前記［５７］または［５８］に記載の分散液。
　［６０］　光重合開始剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、２０重量部以下である前記［５７］または［５８］に記載の分散液。
　［６１］　光重合開始剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１０重量部以下である前記［５７］または［５８］に記載の分散液。
　［６２］　光重合開始剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、５重量部以下である前記［５７］または［５８］に記載の分散液。 [57] The dispersion according to any one of [1] to [56], further comprising a photopolymerization initiator.
[58] The dispersion according to [57], wherein the amount of the photopolymerization initiator is 0.01 parts by weight or more with respect to 100 parts by weight as a total of the chlorinated rubber and the compound having a polymerizable group.
[59] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 40 parts by weight or less based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[60] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 20 parts by weight or less with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
[61] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 10 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[62] The dispersion according to [57] or [58], wherein the amount of the photopolymerization initiator is 5 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
　［６３］　さらに蛍光増白剤を含む前記［１］～［６２］のいずれか一つに記載の分散液。
　［６４］　蛍光増白剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して０．０１重量部以上である前記［６３］に記載の分散液。
　［６５］　蛍光増白剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、５重量部以下である前記［６３］または［６４］に記載の分散液。
　［６６］　蛍光増白剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、３重量部以下である前記［６３］または［６４］に記載の分散液。
　［６７］　蛍光増白剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１重量部以下である前記［６３］または［６４］に記載の分散液。 [63] The dispersion according to any one of [1] to [62], further comprising a fluorescent brightening agent.
[64] The dispersion liquid according to [63], wherein the amount of the fluorescent brightening agent is 0.01 parts by weight or more with respect to 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group.
[65] The dispersion liquid according to [63] or [64], wherein the amount of the fluorescent brightening agent is 5 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[66] The dispersion according to [63] or [64], wherein the amount of the fluorescent brightening agent is 3 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[67] The dispersion according to [63] or [64], wherein the amount of the optical brightener is 1 part by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
　［６８］　さらにレベリング剤を含む前記［１］～［６７］のいずれか一つに記載の分散液。
　［６９］　レベリング剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１重量部以上である前記［６８］に記載の分散液。
　［７０］　レベリング剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、２０重量部以下である前記［６８］または［６９］に記載の分散液。
　［７１］　レベリング剤の量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１０重量部以下である前記［６８］または［６９］に記載の分散液。 [68] The dispersion according to any one of [1] to [67], further including a leveling agent.
[69] The dispersion according to [68], wherein the amount of the leveling agent is 1 part by weight or more with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group.
[70] The dispersion according to [68] or [69], wherein the amount of the leveling agent is 20 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
[71] The dispersion according to [68] or [69], wherein the amount of the leveling agent is 10 parts by weight or less with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
　［７２］　分散液中の分散質の体積基準のメジアン径が、１０μｍ以下である前記［１］～［７１］のいずれか一つに記載の分散液。
　［７３］　分散液中の分散質の体積基準のメジアン径が、０．０１～５μｍである前記［１］～［７１］のいずれか一つに記載の分散液。
　［７４］　分散液中の分散質の体積基準のメジアン径が０．０１～２μｍである前記［１］～［７１］のいずれか一つに記載の分散液。
　［７５］　分散液中の分散質の体積基準のメジアン径が、０．０１～１μｍである前記［１］～［７１］のいずれか一つに記載の分散液。 [72] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 10 μm or less.
[73] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 5 μm.
[74] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 2 μm.
[75] The dispersion according to any one of [1] to [71], wherein the volume-based median diameter of the dispersoid in the dispersion is 0.01 to 1 μm.
　［７６］　塩素化ゴムが、カルボキシ基およびカルボン酸無水物構造を有さない塩素化ゴムである前記［１］～［７５］のいずれか一つに記載の分散液。 [76] The dispersion according to any one of [1] to [75], wherein the chlorinated rubber is a chlorinated rubber having no carboxy group and no carboxylic anhydride structure.
　［７７］　前記［１］～［７６］のいずれか一つに記載の分散液から形成される塗膜。
　［７８］　前記［７７］に記載の塗膜の硬化物。 [77] A coating film formed from the dispersion according to any one of [1] to [76].
[78] A cured product of the coating film according to [77].
　［７９］　第１の基材と、前記［７８］に記載の硬化物と、接着剤層と、第２の基材とが、この順に積層されている積層体。
　［８０］　第１の基材が、オレフィン系重合体またはエチレン－酢酸ビニル共重合体からなる前記［７９］に記載の積層体。 [79] A laminate in which the first substrate, the cured product according to [78], the adhesive layer, and the second substrate are stacked in this order.
[80] The laminate according to [79], wherein the first base material is made of an olefin polymer or an ethylene-vinyl acetate copolymer.
　本発明の分散液は、長期保存後に使用しても、充分な強度で被着体に対して接着することができる。 The dispersion of the present invention can adhere to an adherend with sufficient strength even when used after long-term storage.
＜分散液＞
　本発明の分散液は、分散媒として水を含み、分散質として塩素化ゴムおよび重合性基を有する化合物を含む。本発明の分散液は、水系接着剤、プライマーまたはそれらの原料として有用である。 <Dispersion>
The dispersion of the present invention contains water as a dispersion medium, and contains a chlorinated rubber and a compound having a polymerizable group as a dispersoid. The dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
　本発明の分散液（ディスパージョン）は、分散質が固体状である懸濁液（サスペンジョン）でもよく、分散質が液状である乳濁液（エマルション）でもよく、一部の分散質が固体状であり、残りの分散質が液状である分散液であってもよい。本発明の分散液は、好ましくは分散質が液状である乳濁液であるか、または一部の分散質が固体状であり、残りの分散質が液状である分散液であり、より好ましくは分散質が液状である乳濁液である。 The dispersion (dispersion) of the present invention may be a suspension (suspension) in which the dispersoid is solid, or may be an emulsion (emulsion) in which the dispersoid is liquid, and some of the dispersoid is solid. The remaining dispersoid may be a liquid dispersion. The dispersion of the present invention is preferably an emulsion in which the dispersoid is a liquid, or a part of the dispersoid is a solid and the remaining dispersoid is a liquid, more preferably An emulsion in which the dispersoid is liquid.
　本発明の分散液において、塩素化ゴムの少なくとも一部が、液状の分散質中に溶解していることが好ましい。ここで、塩素化ゴムの少なくとも一部が液状の分散質に溶解しているとは、分散液を孔径０．５０μｍ程度のフィルターで濾過した際に、塩素化ゴムの少なくとも一部が濾液中に含まれていることを意味する。濾液中に含まれる塩素化ゴムは、濾過前の分散液に含まれる塩素化ゴム１００重量部に対して、好ましくは１重量部以上、より好ましくは１０重量部以上、さらに好ましくは３０重量部以上、より一層好ましくは７０重量部以上である。塩素化ゴムの全部が液状の分散質中に溶解していること（即ち、塩素化ゴムの全部が濾液中に含まれること）が特に好ましい。 In the dispersion of the present invention, it is preferable that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid. Here, that at least a part of the chlorinated rubber is dissolved in the liquid dispersoid means that when the dispersion is filtered through a filter having a pore size of about 0.50 μm, at least a part of the chlorinated rubber is in the filtrate. Means included. The chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
　本発明の分散液において、重合性基を有する化合物の少なくとも一部が、２３℃および大気圧下にて液状であることが好ましく、重合性基を有する化合物の全部が、２３℃および大気圧下にて液状であることがより好ましい。この態様において、塩素化ゴムの少なくとも一部が、２３℃および大気圧下にて液状である重合性基を有する化合物（以下「液状である重合性基を有する化合物」と略称することがある）中に溶解していることが好ましく、塩素化ゴムの全部が、液状である重合性基を有する化合物中に溶解していることがより好ましい。 In the dispersion of the present invention, it is preferable that at least a part of the compound having a polymerizable group is liquid at 23 ° C. and atmospheric pressure, and all the compounds having a polymerizable group are at 23 ° C. and atmospheric pressure. More preferably, it is liquid. In this embodiment, at least a part of the chlorinated rubber has a polymerizable group that is liquid at 23 ° C. and atmospheric pressure (hereinafter sometimes abbreviated as “compound having a polymerizable group that is liquid”). It is preferable that the chlorinated rubber is dissolved in the solvent, and it is more preferable that the entire chlorinated rubber is dissolved in the compound having a polymerizable group that is liquid.
　塩素化ゴムの少なくとも一部が液状である重合性基を有する化合物に溶解しているとは、塩素化ゴムと液状である重合性基を有する化合物との混合物を孔径０．５０μｍ程度のフィルターで濾過した際に、塩素化ゴムの少なくとも一部が濾液中に含まれていることを意味する。濾液中に含まれる塩素化ゴムは、濾過前の分散液に含まれる塩素化ゴム１００重量部に対して、好ましくは１重量部以上、より好ましくは１０重量部以上、さらに好ましくは３０重量部以上、より一層好ましくは７０重量部以上である。塩素化ゴムの全部が液状の分散質中に溶解していること（即ち、塩素化ゴムの全部が濾液中に含まれること）が特に好ましい。 The fact that at least a part of chlorinated rubber is dissolved in a compound having a polymerizable group that is liquid means that a mixture of a chlorinated rubber and a compound having a polymerizable group that is liquid is filtered with a filter having a pore diameter of about 0.50 μm. It means that at least a part of the chlorinated rubber is contained in the filtrate when filtered. The chlorinated rubber contained in the filtrate is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and further preferably 30 parts by weight or more with respect to 100 parts by weight of the chlorinated rubber contained in the dispersion before filtration. More preferably, it is 70 parts by weight or more. It is particularly preferable that all of the chlorinated rubber is dissolved in the liquid dispersoid (that is, all of the chlorinated rubber is contained in the filtrate).
　塩素化ゴムと重合性基を有する化合物との混合物を調製する際の混合温度は、通常２５～１００℃であり、その混合時間は、可能な限り短時間が好ましい。このために用いられる混合機としては、例えば、バンバリーミキサー、ヘンシェルミキサー、ホモミキサー等が挙げられる。 The mixing temperature for preparing the mixture of the chlorinated rubber and the compound having a polymerizable group is usually 25 to 100 ° C., and the mixing time is preferably as short as possible. Examples of the mixer used for this purpose include a Banbury mixer, a Henschel mixer, and a homomixer.
　塩素化ゴムおよび重合性基を有する化合物の合計量は、塩素化ゴム、重合性基を有する化合物および水の合計中に、１～６０重量％、好ましくは３～３０重量％、より好ましくは５～１５重量％である。塩素化ゴムおよび重合性基を有する化合物の合計量を、上記範囲内とすることにより、接着性が良好となる。 The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight, preferably 3 to 30% by weight, more preferably 5% in the total of the chlorinated rubber, the compound having a polymerizable group and water. ~ 15 wt%. Adhesiveness will become favorable by making the total amount of the compound which has chlorinated rubber and a polymeric group into the said range.
　本発明の分散液は、３０ｍＬの分散液を１００ｍＬ容器に注ぎ、自転公転撹拌機を用いて、自転速度８００ｒｐｍおよび公転速度２，０００ｒｐｍの条件で１分間撹拌して測定試料を調製し、２０ｍＬの測定試料を直径２５ｍｍのシリンダー状の試料セルに注ぎ、試料セル中の測定試料に波長が８８０ｎｍである入射光を照射し、入射光に対して４５°の位置で測定試料からの後方散乱光を検出することによる後方散乱光強度（％）の測定を、測定試料の調製から１０分以内に開始し、試料セル中の測定試料の上部、中間部および底部のそれぞれにおける、測定を開始してから３０分後に測定した後方散乱光強度（％）に対する、測定を開始してから２４時間後に測定した後方散乱光強度（％）の変化量の絶対値における最大値α（％）が、下記式（I）～（III）：
α（上部）　＜２０　　　（I）
α（中間部）＜５　　　　（II）
α（底部）　＜１０　　　（III）
［式中、α（上部）は、測定試料の上部における前記最大値α（％）を示し、α（中間部）は、測定試料の中間部における前記最大値α（％）を示し、α（底部）は、測定試料の底部における前記最大値α（％）を示し、測定試料の上部、中間部および底部は、それぞれ、メニスカスの部分を除いた試料セル中の測定試料の高さを上から１／３ずつ分割した測定試料の部分を示す。］
の要件を満たすことを特徴の一つとする。なお、本発明において、測定試料の上部と中間部との境界、および測定試料の中間部と底部との境界は、いずれも、測定試料の中間部に含まれる。このような要件を満たす本発明の分散液は、長期保存後に使用しても、充分な強度で被着体に対して接着することができる。 The dispersion of the present invention was prepared by pouring 30 mL of the dispersion into a 100 mL container, and stirring for 1 minute under the conditions of a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer. The measurement sample is poured into a cylindrical sample cell having a diameter of 25 mm, the measurement sample in the sample cell is irradiated with incident light having a wavelength of 880 nm, and backscattered light from the measurement sample is emitted at a position of 45 ° with respect to the incident light. The measurement of the backscattered light intensity (%) by detection is started within 10 minutes from the preparation of the measurement sample, and the measurement is started at each of the top, middle and bottom of the measurement sample in the sample cell. The maximum value α (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the backscattered light intensity (%) measured 30 minutes later is Formulas (I) to (III):
α (upper part) <20 (I)
α (intermediate part) <5 (II)
α (bottom) <10 (III)
[Wherein, α (upper part) represents the maximum value α (%) at the upper part of the measurement sample, α (middle part) represents the maximum value α (%) at the intermediate part of the measurement sample, and α ( Bottom) shows the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion from the top. The part of the measurement sample divided by 1/3 is shown. ]
One of the characteristics is to satisfy the above requirements. In the present invention, the boundary between the upper part and the intermediate part of the measurement sample and the boundary between the intermediate part and the bottom part of the measurement sample are all included in the intermediate part of the measurement sample. Even if the dispersion liquid of the present invention satisfying such requirements is used after long-term storage, it can adhere to an adherend with sufficient strength.
　前記測定試料の調製および前記後方散乱光強度（％）の測定からなる一連の操作は、２４～２６℃の環境下に置かれた装置を用いて２４～２６℃の環境下で実施される。なお、測定試料の調製（即ち、自転公転撹拌機による分散液の撹拌）には、２４～２６℃の環境下で１時間以上静置した分散液を使用する。 A series of operations consisting of preparation of the measurement sample and measurement of the backscattered light intensity (%) is performed in an environment at 24-26 ° C. using an apparatus placed in an environment at 24-26 ° C. For the preparation of the measurement sample (that is, stirring of the dispersion liquid using a rotation / revolution stirrer), a dispersion liquid that is allowed to stand for 1 hour or more in an environment of 24 to 26 ° C. is used.
　前記測定試料を調製するための自転公転撹拌機としては、例えば、シンキー社製「自転・公転ミキサー　あわとり練太郎　ＡＲＥ－３１０」が挙げられる。前記測定試料の後方散乱光強度（％）の変化量を測定する装置としては、例えば、Ｆｏｒｍｕｌａｔｉｏｎ社製の「タービスキャンＴＯＷＥＲ」が挙げられる。 Examples of the rotation / revolution stirrer for preparing the measurement sample include “Rotation / revolution mixer: Awatori Nertaro ARE-310” manufactured by Sinky Corporation. As an apparatus for measuring the amount of change in the backscattered light intensity (%) of the measurement sample, for example, “turbiscan TOWER” manufactured by Formulation may be mentioned.
　前記「後方散乱光強度（％）」とは、「照射した入射光の強度に対する検出された後方散乱光の強度（％）」を意味する。前記「測定を開始してから３０分後に測定した後方散乱光強度（％）に対する、測定を開始してから２４時間後に測定した後方散乱光強度（％）の変化量」とは、「測定を開始してから３０分後に測定した後方散乱光強度（％）と、測定を開始してから２４時間後に測定した後方散乱光強度（％）との差」を意味する。前記「絶対値における最大値」とは、「試料セル中の測定試料の上部、中間部および底部のそれぞれにおいて算出される、複数の前記絶対値における最大値」を意味する。 The “backscattered light intensity (%)” means “intensity of detected backscattered light with respect to the intensity of irradiated incident light (%)”. “The amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement” means “measurement It means a difference between the backscattered light intensity (%) measured 30 minutes after the start and the backscattered light intensity (%) measured 24 hours after the start of measurement. The “maximum value in absolute value” means “a maximum value in a plurality of the absolute values calculated in each of the top, middle, and bottom of the measurement sample in the sample cell”.
　分散液中の分散質の体積基準のメジアン径は、好ましくは１０μｍ以下であり、より好ましくは０．０１～５μｍであり、さらに好ましくは０．０１～２μｍであり、さらに一層好ましくは０．０１～１μｍである。メジアン径が上記範囲内であると、分散液の静置安定性が良好となる。 The volume-based median diameter of the dispersoid in the dispersion is preferably 10 μm or less, more preferably 0.01 to 5 μm, still more preferably 0.01 to 2 μm, and still more preferably 0.01 ~ 1 μm. When the median diameter is within the above range, the standing stability of the dispersion is good.
　分散質の体積基準のメジアン径とは、積算粒子径分布の値が、体積基準で５０％となる粒子径を意味する。このメジアン径は、ＨＯＲＩＢＡ製作所製、レーザー回折粒子径測定装置ＬＡ－９５０Ｖ２で測定することができる。 The volume-based median diameter of the dispersoid means a particle diameter at which the integrated particle diameter distribution value is 50% on the volume basis. This median diameter can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA.
＜塩素化ゴム＞
　塩素化ゴムとは、天然ゴムまたは合成ゴムを塩素化したものを意味する。塩素化ゴムは、１種でもよいし、２種以上でもよい。なお、本明細書において「ゴム」とは、特段の記載が無い限り、「未架橋ゴム」を意味する。 <Chlorinated rubber>
Chlorinated rubber means chlorinated natural rubber or synthetic rubber. The chlorinated rubber may be one type or two or more types. In the present specification, “rubber” means “uncrosslinked rubber” unless otherwise specified.
　結晶性の低い塩素化ゴムは、融点を有さないものがある。本発明で使用する塩素化ゴムとしては、融点を有する塩素化ゴムでもよく、融点を有さない塩素化ゴムでもよい。融点を有する塩素化ゴムを使用することが好ましい。塩素化ゴムの融点は、好ましくは１００℃以上、より好ましくは２００℃以上、さらに好ましくは２４０℃以上であり、好ましくは３５０℃以下、より好ましくは３００℃以下である。塩素化ゴムの融点は、示差走査熱量計（ＤＳＣ）によって測定することができる。ＤＳＣの装置としては、例えば、島津製作所社製ＤＳＣ－６０Ｐｌｕｓが挙げられる。 Some chlorinated rubbers with low crystallinity do not have a melting point. The chlorinated rubber used in the present invention may be a chlorinated rubber having a melting point or a chlorinated rubber having no melting point. It is preferable to use a chlorinated rubber having a melting point. The melting point of the chlorinated rubber is preferably 100 ° C. or higher, more preferably 200 ° C. or higher, further preferably 240 ° C. or higher, preferably 350 ° C. or lower, more preferably 300 ° C. or lower. The melting point of the chlorinated rubber can be measured by a differential scanning calorimeter (DSC). An example of the DSC apparatus is DSC-60 Plus manufactured by Shimadzu Corporation.
　塩素化ゴムの塩素原子含有量は、好ましくは４５重量％以上、より好ましくは４５～８５重量％、さらに好ましくは５５～８０重量％である。 The chlorine atom content of the chlorinated rubber is preferably 45% by weight or more, more preferably 45 to 85% by weight, still more preferably 55 to 80% by weight.
　塩素化ゴムとしては、カルボキシ基およびカルボン酸無水物構造を有さないものを用いることが好ましい。このような塩素化ゴムを含有する本発明の分散液を水系接着剤、プライマーまたはそれらの原料として使用した場合、その塗膜の耐水性の低下の懸念はきわめて小さくなり、有効である。 As the chlorinated rubber, those having no carboxy group and carboxylic anhydride structure are preferably used. When the dispersion liquid of the present invention containing such a chlorinated rubber is used as an aqueous adhesive, primer or raw material thereof, the concern about the decrease in water resistance of the coating film is extremely small and effective.
　塩素化ゴムは、天然ゴムまたは合成ゴムを塩素化したものであれば特に限定されないが、例えば、塩素化天然ゴム、塩素化ブタジエンゴム、塩素化ブチルゴム、塩素化イソプレンゴム、ブタジエン／塩素化環状共役ジエン付加物、塩素化ブタジエンスチレン共重合体、臭素化ポリ（２，３－ジクロロ－１，３－ブタジエン）およびα－ハロアクリロニトリル－ｃｏ－２，３－ジクロロ－１，３－ブタジエン共重合体等が挙げられる。炭素数が４以上のモノマーを含む原料から合成される塩素化ゴムが好ましい。塩素化ゴムは、より好ましくは塩素化天然ゴム、塩素化イソプレンゴムおよび塩素化ブタジエンゴムからなる群から選ばれる少なくとも一つであり、さらに好ましくは塩素化天然ゴム、塩素化イソプレンゴムまたは塩素化ブタジエンゴムである。 The chlorinated rubber is not particularly limited as long as it is chlorinated natural rubber or synthetic rubber. For example, chlorinated natural rubber, chlorinated butadiene rubber, chlorinated butyl rubber, chlorinated isoprene rubber, butadiene / chlorinated cyclic conjugate Diene adducts, chlorinated butadiene styrene copolymers, brominated poly (2,3-dichloro-1,3-butadiene) and α-haloacrylonitrile-co-2,3-dichloro-1,3-butadiene copolymers Etc. A chlorinated rubber synthesized from a raw material containing a monomer having 4 or more carbon atoms is preferred. The chlorinated rubber is more preferably at least one selected from the group consisting of chlorinated natural rubber, chlorinated isoprene rubber and chlorinated butadiene rubber, more preferably chlorinated natural rubber, chlorinated isoprene rubber or chlorinated butadiene. It is rubber.
　天然ゴムまたは合成ゴムを塩素化する方法としては、従来公知の方法を採用することができる。例えば、天然ゴムまたは合成ゴムを四塩化炭素、モノクロルベンゼン等の塩素化有機溶剤またはトルエン等の有機溶剤に溶解し、塩素ガスを吹き込む方法；天然ゴムまたは合成ゴムを水に懸濁または乳化した状態で塩素ガスを吹き込む方法；天然ゴムまたは合成ゴムを水に懸濁または乳化した状態で紫外線を照射しつつ塩素ガスを導入する方法；低温加圧下において、天然ゴムまたは合成ゴムと液体塩素とを接触させて直接的に塩素化する方法等が挙げられる。また、凝集固体化した天然ゴムまたは合成ゴムを有機溶剤に溶解した後、塩素化してもよいし、凝集固体化した天然ゴムまたは合成ゴムを有機溶剤に溶解後、乳化分散し、溶剤を揮発させた状態で塩素化することもできる。天然ゴムを塩素化する場合、ラテックス状の天然ゴムに塩素ガスを吹き込んで塩素化することもできる。例えば、水に、ポリイソプレンと、界面活性剤と、塩酸、硫酸または硝酸等の酸とを加え、乳化した後、塩素ガスを吹き込むことで均一に塩素化したポリイソプレンを得ることができる。 As a method of chlorinating natural rubber or synthetic rubber, a conventionally known method can be adopted. For example, a method in which natural rubber or synthetic rubber is dissolved in a chlorinated organic solvent such as carbon tetrachloride or monochlorobenzene, or an organic solvent such as toluene, and chlorine gas is blown; the natural rubber or synthetic rubber is suspended or emulsified in water Injecting chlorine gas with water; Introducing chlorine gas while irradiating ultraviolet rays with natural rubber or synthetic rubber suspended or emulsified in water; Contacting natural rubber or synthetic rubber with liquid chlorine under low pressure And chlorinating directly. In addition, the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then chlorinated, or the aggregated and solidified natural rubber or synthetic rubber may be dissolved in an organic solvent and then emulsified and dispersed to volatilize the solvent. It can also be chlorinated in a wet state. When natural rubber is chlorinated, it can be chlorinated by blowing chlorine gas into latex natural rubber. For example, polyisoprene, a surfactant, and an acid such as hydrochloric acid, sulfuric acid, or nitric acid are added to water and emulsified, and then uniformly chlorinated polyisoprene can be obtained by blowing chlorine gas.
　塩素化ゴムのポリスチレン換算の重量平均分子量（Ｍｗ）は、好ましくは１，０００以上、より好ましくは３，０００以上、さらに好ましくは５，０００以上、特に好ましくは１０，０００以上であり、好ましくは４００，０００以下、より好ましくは２００，０００以下である。このＭｗは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定することができる。このようなＭｗを有する塩素化ゴムを含有する本発明の分散液を、水系接着剤、プライマーまたはそれらの原料として用いた場合、充分な接着強度を確保することができるとともに、粘度の過度の上昇を抑制して、被着体に対する接着性を充分に確保することができる。 The polystyrene-reduced weight average molecular weight (Mw) of the chlorinated rubber is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, particularly preferably 10,000 or more, preferably 400,000 or less, more preferably 200,000 or less. This Mw can be measured by gel permeation chromatography (GPC). When the dispersion liquid of the present invention containing such a chlorinated rubber having Mw is used as an aqueous adhesive, primer or raw material thereof, sufficient adhesive strength can be ensured and the viscosity is excessively increased. Can be suppressed and sufficient adhesion to the adherend can be secured.
　塩素化ゴムとしては、例えば、市販品および公知の方法またはそれに準じて製造したものを使用することができる。市販品としては、例えば、スーパークロン（登録商標）ＣＲ－１０、ＣＲ－２０（日本製紙（株））、ペルグートＳ－５、ペルグートＳ－１０、ペルグートＳ－２０、ペルグートＳ－４０、ペルグートＳ－９０、ペルグートＳ－１３０、ペルグートＳ－１７０（コベストロ社）、Ａｌｌｏｐｒｅｎｅ（登録商標）Ｒ１０，Ｒ２０，Ｒ４０（ＩＣＩ　ＵＫ製）等が挙げられる。公知の方法としては、例えば、特許第２６６０４７８号に記載の方法が挙げられる。 As the chlorinated rubber, for example, commercially available products and known methods or those manufactured according to the methods can be used. Commercially available products include, for example, Supercron (registered trademark) CR-10, CR-20 (Nippon Paper Industries Co., Ltd.), Pergut S-5, Pergut S-10, Pergut S-20, Pergut S-40, Pergut S -90, Pergut S-130, Pergut S-170 (Covestro), Alloprene (registered trademark) R10, R20, R40 (manufactured by ICI UK). As a well-known method, the method of patent 2660478 is mentioned, for example.
　塩素化ゴムの量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは１～３０重量部、より好ましくは３～２５重量部、さらに好ましくは５～２０重量部である。 The amount of the chlorinated rubber is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, still more preferably 5 to 20 parts by weight based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part.
　塩素化ゴムの量は、塩素化ゴム、重合性基を有する化合物および水の合計中に、好ましくは０．０１～１８重量％、より好ましくは０．１～１０重量％、さらに好ましくは０．２～５重量％である。 The amount of the chlorinated rubber is preferably 0.01 to 18% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1% by weight in the total of the chlorinated rubber, the compound having a polymerizable group and water. 2 to 5% by weight.
＜重合性基を有する化合物＞
　重合性基を有する化合物は、１種のみを使用してもよく、２種以上を併用してもよい。また、該化合物が有する重合性基は、一つでもよく、二つ以上でもよい。また、該化合物は、１種のみの重合性基を有していてもよく、２種以上の重合性基を有していてもよい。重合性基としては、例えば、ビニル基、アリル基、プロぺニル基、ビニリデン基、ビニレン基、（メタ）アクリル基、（メタ）アクリロイル基、ビニルエーテル基、ビニルベンジルエーテル基、（メタ）アクリルオキシ基、（メタ）アクリルアミド基、スチリルオキシ基、スチリルアミド基、イソシアネート基、チオイソシアネート基、カルボキシル基、アルコール性またはフェノール性水酸基、シラノール基、エポキシ基、グリシジル基、環状エーテル基（例、オキセタン基）等の開環重合性基が挙げられる。なお、本明細書中、「（メタ）アクリル」とは「アクリルおよびメタクリル」を意味し、「（メタ）アクリロイル」とは、「アクリロイルおよびメタクリロイル」を意味する。他の「（メタ）」の表現も同様の意味である。 <Compound having a polymerizable group>
Only 1 type may be used for the compound which has a polymeric group, and 2 or more types may be used together. Moreover, the polymeric group which this compound has may be one, and two or more may be sufficient as it. Moreover, this compound may have only 1 type of polymeric group, and may have 2 or more types of polymeric groups. Examples of the polymerizable group include a vinyl group, an allyl group, a propenyl group, a vinylidene group, a vinylene group, a (meth) acryl group, a (meth) acryloyl group, a vinyl ether group, a vinyl benzyl ether group, and a (meth) acryloxy group. Group, (meth) acrylamide group, styryloxy group, styrylamide group, isocyanate group, thioisocyanate group, carboxyl group, alcoholic or phenolic hydroxyl group, silanol group, epoxy group, glycidyl group, cyclic ether group (eg, oxetane group) ) And the like. In the present specification, “(meth) acryl” means “acryl and methacryl”, and “(meth) acryloyl” means “acryloyl and methacryloyl”. Other expressions of “(meta)” have the same meaning.
　重合性基を有する化合物は、好ましくはエチレン性不飽和結合を有する化合物、エポキシ化合物、およびオキセタン化合物からなる群から選ばれる少なくとも一つであり、より好ましくはエチレン性不飽和結合を有する化合物である。エチレン性不飽和結合を有する化合物中のエチレン性不飽和結合の数は、好ましくは１～３、より好ましくは１～２である。 The compound having a polymerizable group is preferably at least one selected from the group consisting of a compound having an ethylenically unsaturated bond, an epoxy compound, and an oxetane compound, and more preferably a compound having an ethylenically unsaturated bond. . The number of ethylenically unsaturated bonds in the compound having an ethylenically unsaturated bond is preferably 1 to 3, more preferably 1 to 2.
　エチレン性不飽和結合を１個有する化合物としては、例えば、複素環式エチレン性不飽和化合物（例えば、Ｎ－ビニルピロリドン、Ｎ－ビニルピリジンおよびＮ－ビニルカプロラクタム等のＮ－ビニル－窒素含有複素環化合物、モルホリン（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレートおよびグリシジル（メタ）アクリレート等の複素環式（メタ）アクリレート）、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、ジアルキルアミノエチル（メタ）アクリレート（例えば、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等）、Ｎ，Ｎ’－ジメチルアクリルアミド、アルコキシ（ポリ）アルキレングリコール　（メタ）アクリレート（例えば、メトキシエチレン（メタ）アクリレート、エトキシ－ジエチレングリコール　（メタ）アクリレート、メトキシポリエチレン（メタ）アクリレート、ブトキシポリエチレン（メタ）アクリレート等）、アルキル（メタ）アクリレート（例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ステアリル（メタ）アクリレート、セチル（メタ）アクリレート、ベヘニル（メタ）アクリレート等）、ヒドロキシル基含有（メタ）アクリレート（例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチルフタル酸、グリセリンモノ（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、ペンタンジオール　モノ（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリロイルホスフェート、ネオペンチルグリコール　モノ（メタ）アクリレート、ポリプロピレングリコール　モノ（メタ）アクリレート、ポリエチレングリコール　モノ（メタ）アクリレート、ポリエチレングリコール－プロピレングリコール　モノ（メタ）アクリレート等）、ポリε－カプロラクトンモノ（メタ）アクリレート、モノ［２－（メタ）アクリロイルオキシエチル］アシッドホスフェート、ハロゲン含有（メタ）アクリレート（例えば、トルフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート、Ｎ，Ｎ，Ｎ－トリメチル－Ｎ－（２－ヒドロキシ―３メタクリロイルオキシプロピル）－アンモニウムクロライド等）、シリコーン含有（メタ）アクリレート（例えば、（メタ）アクリル変性オルガノポリシロキサン、３－（メタ）アクリルオキシプロピルトリメトキシシラン、３－（メタ）アクリルオキシプロピルトリエトキシシラン、３－（メタ）アクリルオキシプロピルメチルジメトキシシラン、３－（メタ）アクリルオキシプロピルメチルジエトキシシラン等）、不飽和カルボン酸グリシジルエステル含有（メタ）アクリレート（例えば、グリシジル（メタ）アクリレート、グリシジルメタクリレート、３，４－エポキシブチル（メタ）アクリレート、（３，４－エポキシシクロヘキシル）メチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等）、脂肪族ビニル化合物（例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ビニルメチルエーテル、ビニルエチルエーテル、アリルグリシジルエーテル等）、不飽和アミドまたは不飽和イミド類（例えば、アクリルアミド、メタクリルアミド、ジアセトン（メタ）アクリルアミド、α－クロロアクリルアミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－（メタ）アクリロイルフタルイミド、Ｎ－（２－ヒドロキシエチル）アクリルアミド、Ｎ－（２－ヒドロキシエチル）メタクリルアミドおよびマレイミド等）、アクリロニトリル、メタクリロニトリル、α－クロロアクリロニトリル、並びに、重合体（例えは、ポリスチレン、ポリメチルアクリレート、ポリメチルメタクリレート、ポリｎ－ブチルアクリレート、ポリｎ－ブチルメタクリレート、ポリシリコーン等）の末端にモノアクリロイル基またはモノメタクリロイル基を有するマクロモノマー等が挙げられる。 Examples of the compound having one ethylenically unsaturated bond include heterocyclic ethylenically unsaturated compounds (for example, N-vinyl-nitrogen-containing heterocycles such as N-vinylpyrrolidone, N-vinylpyridine and N-vinylcaprolactam). Compounds, heterocyclic (meth) acrylates such as morpholine (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and glycidyl (meth) acrylate), N-vinylformamide, N-vinylacetamide, dialkylaminoethyl (meth) acrylate ( For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.), N, N′-dimethylacrylamide, alkoxy (poly) alkylene glycol (meth) acrylate (for example, methoxyethylene (meta) Acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxypolyethylene (meth) acrylate, butoxypolyethylene (meth) acrylate, etc.), alkyl (meth) acrylate (for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl ( (Meth) acrylate, i-propyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, Decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (Meth) acrylate, stearyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, etc.), hydroxyl group-containing (meth) acrylate (eg 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth)) Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, glycerin mono (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, pentanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, neopentyl glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol-propylene glycol mono (meth) acrylate, etc.), poly ε-caprolactone mono (meth) acrylate, mono [2- (meth) acryloyloxyethyl] acid phosphate Halogen-containing (meth) acrylates (eg, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, N, N, N-trimethyl) -N- (2-hydroxy-3methacryloyloxypropyl) -ammonium chloride, etc.), silicone-containing (meth) acrylates (eg (meth) acryl-modified organopolysiloxanes, 3- (meth) acrylates) Yloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane), unsaturated carboxylic acid Glycidyl ester-containing (meth) acrylates (eg glycidyl (meth) acrylate, glycidyl methacrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate glycidyl ether), aliphatic vinyl compounds (eg vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether), unsaturated amides Or unsaturated imides (eg, acrylamide, methacrylamide, diacetone (meth) acrylamide, α-chloroacrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, N- (meth) acryloylphthalimide, N- (2-hydroxyethyl) Acrylamide, N- (2-hydroxyethyl) methacrylamide and maleimide), acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and polymers (eg, polystyrene, polymethyl acrylate, polymethyl methacrylate, poly n-butyl) Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of an acrylate, poly n-butyl methacrylate, polysilicone and the like.
　エチレン性不飽和結合を１個有し、且つ環状構造を有する化合物としては、例えば、脂環式骨格を有する（メタ）アクリレート（例えば、シクロヘキシル（メタ）アクリレート、４（１，１－ジメチルエチル）シクロヘキシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、３，３，５－トリメチルシクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ノルボルニルメチル（メタ）アクリレート、フェニルノルボニル（メタ）アクリレート、シアノノルボルニル（メタ）アクリレート、メンチル（メタ）アクリレート、フェンチル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジメチルアダマンチル（メタ）アクリレート、トリシクロ〔５．２．１．０２，６〕デカ－８－イル（メタ）アクリレート、トリシクロ〔５．２．１．０２，６〕デカ－４－メチル（メタ）アクリレート、シクロデシル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、イソボルニル（メタ）アクリレート、ボルニル（メタ）アクリレート、ジシクロペンタジエン（メタ）アクリレート、ジシクロペンテニルオキシアルキル（メタ）アクリレート、トリシクロデカニルオキシエチル（メタ）アクリレート、イソボルミルオキシエチル（メタ）アクリレート等）、アラルキル（メタ）アクリレート（例えば、ベンジル（メタ）アクリレート、ｏ－フェニルフェノールグリシジルエーテル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等）、フェノキシアルキル（メタ）アクリレート（例えば、２－フェノキシエチル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート等）、アルキルフェノキシメチル（メタ）アクリレート（例えば、ノニルフェノキシエチル（メタ）アクリレート等）、フェノキシ（ポリ）アルキレングリコール　（メタ）アクリレート（例えば、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール　（メタ）アクリレート、フェノキシポリエチレングリコール　（メタ）アクリレート等）、アルキルフェノキシ（ポリ）アルキレングリコール　（メタ）アクリレート（例えば、ノニルフェノキシポリエチレングリコール　（メタ）アクリレート、パラクミルフェノキシエチレングリコール　（メタ）アクリレート等）、ヒドロキシル基および脂環式骨格または芳香族骨格含有（メタ）アクリレート（例えば、２－ヒドロキシ－３－フェニルオキシプロピル（メタ）アクリレート、２－ヒドロキシ－ｏ－フェニルフェノールプロピル（メタ）アクリレート、４－ヒドロキシシクロヘキシル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等）、芳香族ビニル化合物（例えば、スチレン、α－メチルスチレン、ｏ－ビニルトルエン、ｍ－ビニルトルエン、ｐ－ビニルトルエン、ｏ－クロルスチレン、ｍ－クロルスチレン、ｐ－クロルスチレン、ｐ－メトキシスチレン、安息香酸ビニル等）が挙げられる。 Examples of the compound having one ethylenically unsaturated bond and having a cyclic structure include (meth) acrylate having an alicyclic skeleton (for example, cyclohexyl (meth) acrylate, 4 (1,1-dimethylethyl)) Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, norbornylmethyl (meth) acrylate, phenylnorbornyl (meth) acrylate, cyanonor Bornyl (meth) acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] dec-8-yl (Meta Acrylate, tricyclo [5.2.1.0 2,6] dec-4-methyl (meth) acrylate, cyclodecyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, isobornyl (meth) acrylate , Bornyl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyalkyl (meth) acrylate, tricyclodecanyloxyethyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, etc.), aralkyl ( (Meth) acrylate (eg, benzyl (meth) acrylate, o-phenylphenol glycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc.), phenoxyalkyl (meth) acrylate Rate (for example, 2-phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, etc.), alkylphenoxymethyl (meth) acrylate (for example, nonylphenoxyethyl (meth) acrylate, etc.), phenoxy (poly) alkylene glycol (meth) ) Acrylates (eg, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, etc.), alkylphenoxy (poly) alkylene glycol (meth) acrylates (eg, nonylphenoxypolyethylene glycol (meth)) Acrylate, paracumylphenoxyethylene glycol (meth) acrylate, etc.), hydroxyl group and alicyclic skeleton or aromatic Case-containing (meth) acrylate (eg, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 2-hydroxy-o-phenylphenolpropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 2-hydroxy- 3-phenoxypropyl (meth) acrylate, etc.), aromatic vinyl compounds (for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-methoxystyrene, vinyl benzoate, etc.).
　エチレン性不飽和結合を２個有する化合物としては、例えば、２，２－ジメチル－３－ヒドロキシプロピル－２，２－ジメチル－３－ヒドロキシプロピオネートのジ（メタ）アクリレート、ポリオキシアルキレングリコール　ジ（メタ）アクリレート（例えば、エチレングリコール　ジ（メタ）アクリレート、ジエチレングリコール　ジ（メタ）アクリレート、トリエチレングリコール　ジ（メタ）アクリレート、テトラエチレングリコール　ジ（メタ）アクリレート、ポリエチレングリコール　ジ（メタ）アクリレート、プロピレングリコール　ジ（メタ）アクリレート、ジプロピレングリコール　ジ（メタ）アクリレート、トリプロピレングリコール　ジ（メタ）アクリレート、ポリプロピレングリコール　ジ（メタ）アクリレート、ポリエチレングリコール－プロピレングリコール　ジ（メタ）アクリレート、ポリテトラメチレングリコール　ジ（メタ）アクリレート、１，３－ブチレングリコール　ジ（メタ）アクリレート、１，４－ブタンジオール　ジ（メタ）アクリレート、ジエチレングリコール　ジ（メタ）アクリレート、１，６－ヘキサンジオール　ジ（メタ）アクリレート、１，９－ノナンジオール　ジ（メタ）アクリレート、１，１０－デカンジオール　ジ（メタ）アクリレート、ネオペンチルグリコール　ジ（メタ）アクリレート、プロポキシ化ネオペンチルグリコール　ジ（メタ）アクリレート、アルコキシ化ネオペンチルグリコール　ジ（メタ）アクリレート、テトラエチレングリコール　ジ（メタ）アクリレート、トリエチレングリコール　ジ（メタ）アクリレート、トリプロピレングリコール　ジ（メタ）アクリレート、ポリエチレングリコール　ジ（メタ）アクリレート、アルコキシ化ヘキサンジオール　ジ（メタ）アクリレート、ペンタンジオール　ジ（メタ）アクリレート、３－メチル－ペンタンジオール　ジ（メタ）アクリレート、グリセリン　ジ（メタ）アクリレート、トリメチロールプロパン　ジ（メタ）アクリレート、ペンタエリスリトール　ジ（メタ）アクリレート等）、シリコーン含有（メタ）アクリレート（例えば、（メタ）アクリル変性オルガノポリシロキサン等）、並びに、ダイアセトンアクリルアマイド等が挙げられる。 Examples of the compound having two ethylenically unsaturated bonds include di (meth) acrylate of 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, polyoxyalkylene glycol di- (Meth) acrylate (for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Liethylene glycol-propylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propoxylated neo Pentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (me ) Acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkoxylated hexanediol di (meth) acrylate, pentanediol di (meth) acrylate, 3-methyl-pentanediol di (meth) acrylate, Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, etc.), silicone-containing (meth) acrylate (for example, (meth) acryl-modified organopolysiloxane), and diacetone An acrylic amide etc. are mentioned.
　エチレン性不飽和結合を２個有し、且つ環状構造を有する化合物としては、例えば、ビスフェノールＡのアルキレンオキサイド（例えば、エチレンオキサイド、プロピレンオキサイド等）付加物のジ（メタ）アクリレート（例えば、２，２－ビス（２－ヒドロキシエトキシフェニル）プロパンのジ（メタ）アクリレート等）、橋架け環式炭化水素基を有するジ（メタ）アクリレート（例えば、シクロヘキサンジメタノール　ジ（メタ）アクリレート、トリシクロデカンジメチロールのジ（メタ）アクリレート（例えば、トリシクロデカンジメタノール　ジ（メタ）アクリレート等）、ジシクロペンタジエン　ジ（メタ）アクリレート等）、二官能性エポキシ樹脂の（メタ）アクリル酸付加物（例えば、２，２－ビス（グリシジルオキシフェニル）プロパンの（メタ）アクリル酸付加物、ビスフェノールＡジグリシジルエーテルメタクリル酸付加物等）が挙げられる。 Examples of the compound having two ethylenically unsaturated bonds and having a cyclic structure include di (meth) acrylates (for example, 2,2) of adducts of alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) of bisphenol A. Di (meth) acrylate of 2-bis (2-hydroxyethoxyphenyl) propane), di (meth) acrylate having a bridged cyclic hydrocarbon group (for example, cyclohexanedimethanol di (meth) acrylate, tricyclodecanedi) Di (meth) acrylate of methylol (for example, tricyclodecane dimethanol di (meth) acrylate), dicyclopentadiene di (meth) acrylate), (meth) acrylic acid adduct of bifunctional epoxy resin (for example, 2,2-bis (glycidyl oxyphe Le) propane (meth) acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, etc.).
　エチレン性不飽和結合を３個以上有する化合物としては、例えば、トリメチロールプロパン　トリ（メタ）アクリレート、ペンタエリスリトール　トリ（メタ）アクリレート、ペンタエリスリトール　テトラ（メタ）アクリレート、ジペンタエリスリトール　ペンタ（メタ）アクリレート、ジペンタエリスリトール　ヘキサ（メタ）アクリレート、ジトリメチロールプロパン　テトラアクリレート、テトラメチロールメタン　トリ（メタ）アクリレート、テトラメチロールメタン　テトラ（メタ）アクリレート、トリス（アクリロイルオキシ）イソシアヌレート、トリス（２－アクリロイルオキシエチル）イソシアヌレート、トリス（２－ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート、トリス（ヒドロキシプロピル）イソシアヌレートのトリ（メタ）アクリレート、トリアリルトリメリット酸、トリアリルイソシアヌレート、およびシリコーン含有（メタ）アクリレート（例えば、（メタ）アクリル変性オルガノポリシロキサン等）等が挙げられる。 Examples of the compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, tris (acryloyloxy) isocyanurate, tris (2-acryloyloxyethyl) isocyanate Nurate, tris (2-hydroxyethyl) isocyanurate, tri (meth) acrylate, tris (hydroxypropyl) Isocyanurate of tri (meth) acrylate, triallyl trimellitate, triallyl isocyanurate, and silicone-containing (meth) acrylate (e.g., (meth) acrylic-modified organopolysiloxane, etc.).
　エチレン性不飽和結合を有する化合物の炭素数は、好ましくは５～２５、より好ましくは６～２３、さらに好ましくは８～２０である。 The number of carbon atoms of the compound having an ethylenically unsaturated bond is preferably 5 to 25, more preferably 6 to 23, and still more preferably 8 to 20.
　エポキシ化合物としては、例えば、フェニルグリシジルエーテル、ｐ－ｔｅｒｔ－ブチルフェニルグリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、１，２－ブチレンオキサイド、１，３－ブタジエンモノオキサイド、１，２－エポキシドデカン、エピクロロヒドリン、１，２－エポキシデカン、スチレンオキサイド、シクロヘキセンオキサイド、３－メタクリロイルオキシメチルシクロヘキセンオキサイド、３－アクリロイルオキシメチルシクロヘキセンオキサイド、３－ビニルシクロヘキセンオキサイド、ビスフェノールＡジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、臭素化ビスフェノールＡジグリシジルエーテル、臭素化ビスフェノールＦジグリシジルエーテル、臭素化ビスフェノールＳジグリシジルエーテル、エポキシノボラック樹脂、水添ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＦジグリシジルエーテル、水添ビスフェノールＳジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキシル－３’，４’－エポキシ－６’－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールのジ（３，４－エポキシシクロヘキシルメチル）エーテル、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル類、１，１，３－テトラデカジエンジオキサイド、リモネンジオキサイド、１，２，７，８－ジエポキシオクタン、１，２，５，６－ジエポキシシクロオクタン等が挙げられる。 Examples of the epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1 , 2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, bisphenol A diglycidyl Ether, neopentyl glycol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycol Diether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl -3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol Di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide , Limonene dioxide, 1,2,7,8-diepoxyoctane, 1,2,5,6-diepoxycyclooctane, and the like.
　エポキシ化合物としては、硬化速度に優れるという観点から、芳香族エポキシドおよび脂環式エポキシドが好ましく、脂環式エポキシドがより好ましい。 As the epoxy compound, aromatic epoxides and alicyclic epoxides are preferable and alicyclic epoxides are more preferable from the viewpoint of excellent curing speed.
　オキセタン化合物としては、例えば、２－ヒドロキシメチル－２－メチルオキセタン、２－ヒドロキシメチル－２－エチルオキセタン、２－ヒドロキシメチル－２－プロピルオキセタン、２－ヒドロキシメチル－２－ブチルオキセタン、１，４－ビス〔（３－エチル－３－オキセタニルメトキシ）メチル〕ベンゼン等が挙げられる。 Examples of the oxetane compound include 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-propyloxetane, 2-hydroxymethyl-2-butyloxetane, 1,4 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like.
　重合性基を有する化合物は、２３℃および大気圧下にて、固体または液体のいずれでもよく、好ましくは液体である。 The compound having a polymerizable group may be solid or liquid at 23 ° C. and atmospheric pressure, and is preferably liquid.
　本発明の分散液中の重合性基を有する化合物の量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは７０～９９重量部、より好ましくは７５～９７重量部、さらに好ましくは８０～９５重量部である。 The amount of the compound having a polymerizable group in the dispersion of the present invention is preferably 70 to 99 parts by weight, more preferably 75 to 97 parts, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Part by weight, more preferably 80 to 95 parts by weight.
　重合性基を有する化合物は、重合性基を有し、且つ環状構造を有さない化合物と、重合性基および環状構造を有する化合物との混合物であることが好ましい。 The compound having a polymerizable group is preferably a mixture of a compound having a polymerizable group and not having a cyclic structure and a compound having a polymerizable group and a cyclic structure.
　重合性基を有し、且つ環状構造を有さない化合物は、好ましくは２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、１，６－ヘキサンジオール　ジ（メタ）アクリレート、１，９－ノナンジオール　ジ（メタ）アクリレート、および１，１０－デカンジオール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つであり、より好ましくはドデシル（メタ）アクリレート、および１，６－ヘキサンジオール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つであり、さらに好ましくはドデシルメタクリレート、および１，６－ヘキサンジオール　ジメタクリレートからなる群から選ばれる少なくとも一つである。 The compound having a polymerizable group and having no cyclic structure is preferably 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, 1,6-hexane. It is at least one selected from the group consisting of diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate, and more preferably dodecyl (meth). And at least one selected from the group consisting of acrylate and 1,6-hexanediol di (meth) acrylate, and more preferably at least one selected from the group consisting of dodecyl methacrylate and 1,6-hexanediol dimethacrylate. It is.
　重合性基および環状構造を有する化合物は、好ましくは２－フェノキシエチレングリコール　（メタ）アクリレート、２－フェノキシジエチレングリコール　（メタ）アクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つであり、より好ましくは２－フェノキシエチレングリコール　（メタ）アクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つであり、さらに好ましくは２－フェノキシエチレングリコール　メタクリレート、およびトリシクロデカンジメタノール　ジ（メタ）アクリレートからなる群から選ばれる少なくとも一つである。 The compound having a polymerizable group and a cyclic structure is preferably at least selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. One, more preferably at least one selected from the group consisting of 2-phenoxyethylene glycol (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate, and more preferably 2-phenoxyethylene glycol methacrylate. And at least one selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate.
　重合性基を有する化合物が、重合性基を有し、且つ環状構造を有さない化合物と、重合性基および環状構造を有する化合物との混合物である場合、重合性基を有し、且つ環状構造を有さない化合物の量は、塩素化ゴム、重合性基を有する化合物および水の合計中に、好ましくは０．４～５０重量％、より好ましくは１～２５重量％、さらに好ましくは３～２５重量％であり、重合性基および環状構造を有する化合物の量は、塩素化ゴム、重合性基を有する化合物および水の合計中に、好ましくは０．０１～３０重量％、より好ましくは０．１～１５重量％、さらに好ましくは０．２～５重量％である。 When the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure, the compound has a polymerizable group and is cyclic The amount of the compound having no structure is preferably 0.4 to 50% by weight, more preferably 1 to 25% by weight, and still more preferably 3% in the total of the chlorinated rubber, the compound having a polymerizable group and water. The amount of the compound having a polymerizable group and a cyclic structure is preferably from 0.01 to 30% by weight, more preferably in the total of the chlorinated rubber, the compound having a polymerizable group and water. It is 0.1 to 15% by weight, more preferably 0.2 to 5% by weight.
　重合性基を有する化合物が、重合性基を有し、且つ環状構造を有さない化合物と、重合性基および環状構造を有する化合物との混合物である場合、重合性基を有し、且つ環状構造を有さない化合物の量は、重合性基を有する化合物の合計中に、好ましくは４０～９９重量％であり、より好ましくは６０～９７重量％であり、さらに好ましくは８０～９５重量％であり、重合性基および環状構造を有する化合物の量は、重合性基を有する化合物の合計中に、好ましくは１～６０重量％であり、より好ましくは３～４０重量％であり、さらに好ましくは５～２０重量％である。 When the compound having a polymerizable group is a mixture of a compound having a polymerizable group and not having a cyclic structure, and a compound having a polymerizable group and a cyclic structure, the compound has a polymerizable group and is cyclic The amount of the compound having no structure is preferably 40 to 99% by weight, more preferably 60 to 97% by weight, and still more preferably 80 to 95% by weight in the total of the compounds having a polymerizable group. The amount of the compound having a polymerizable group and a cyclic structure is preferably 1 to 60% by weight, more preferably 3 to 40% by weight, and still more preferably in the total of the compound having a polymerizable group. Is from 5 to 20% by weight.
＜水＞
　本発明の分散液が含有する水としては、特に限定はなく、例えば、水道水または脱イオン水が用いられる。 <Water>
There is no limitation in particular as water which the dispersion liquid of this invention contains, For example, tap water or deionized water is used.
＜他の成分＞
　本発明の分散液は、水、塩素化ゴムおよび重合性基を有する化合物とは異なる他の成分を含有していてもよい。他の成分は、１種のみを使用してもよく、２種以上を併用してもよい。他の成分としては、例えば、重合禁止剤、界面活性剤、光重合開始剤、光安定剤、紫外線硬化性オリゴマー、蛍光増白剤、レベリング剤、塩基性化合物、有機溶剤、架橋剤、光増感剤、塩素化ゴムとは異なる他の樹脂またはゴム、フェノール系安定剤、フォスファイト系安定剤、アミン系安定剤、アミド系安定剤、老化防止剤、耐候安定剤、防腐剤、沈降防止剤、酸化防止剤、熱安定剤、揺変剤、増粘剤、消泡剤、粘度調整剤、耐候剤、顔料分散剤、帯電防止剤、滑剤、核剤、難燃剤、油剤、染料、硬化剤；酸化チタン（ルチル型）および酸化亜鉛等の遷移金属化合物；カーボンブラック等の顔料；ガラス繊維、炭素繊維、チタン酸カリウム繊維、ウオラストナイト、炭酸カルシウム、硫酸カルシウム、タルク、ガラスフレーク、硫酸バリウム、クレー、カオリン、微粉末シリカ、マイカ、珪酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化マグネシウム、およびセライト等の無機または有機の充填剤；等が挙げられる。これらは、いずれも１種のみを使用してもよく、２種以上を併用してもよい。 <Other ingredients>
The dispersion of the present invention may contain other components different from water, chlorinated rubber and the compound having a polymerizable group. Only 1 type may be used for another component and it may use 2 or more types together. Other components include, for example, polymerization inhibitors, surfactants, photopolymerization initiators, light stabilizers, UV curable oligomers, fluorescent brighteners, leveling agents, basic compounds, organic solvents, crosslinking agents, photosensitizers. Sensitizers, other resins or rubbers different from chlorinated rubber, phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, preservatives, anti-settling agents , Antioxidant, heat stabilizer, thixotropic agent, thickener, antifoaming agent, viscosity modifier, weathering agent, pigment dispersant, antistatic agent, lubricant, nucleating agent, flame retardant, oil agent, dye, curing agent Transition metal compounds such as titanium oxide (rutile type) and zinc oxide; pigments such as carbon black; glass fiber, carbon fiber, potassium titanate fiber, wollastonite, calcium carbonate, calcium sulfate, talc, glass flake, barium sulfate , Clay, kaolin, finely divided silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and fillers of inorganic or organic, such as Celite, and the like. Any of these may be used alone or in combination of two or more.
＜重合禁止剤＞
　重合禁止剤に特に限定はなく、公知の重合禁止剤を使用することができる。重合禁止剤としては、例えば、ヒドロキノン、メチルヒドロキノン、ヒドロキノンのモノエステル化物、Ｎ－ニトロソジフェニルアミン、フェノチアジン、４－ｔ－ブチルカテコール、Ｎ－フェニルナフチルアミン、２，６－ジ－ｔ－ブチル－ｐ－メチルフェノール、２，５－ジ－ｔ－ブチルヒドロキノン、１，４－ベンゾキノン、２，６－ジ－ｔ－ブチル－１，４－ベンゾキノン、メチル－ｐ－ベンゾキノン、２，５－ジフェニル－ｐ－ベンゾキノン、４－メトキシフェノール、クロラニール、ピロガロール、２－オキシジフェニルアミン、フェノチアジン等が挙げられる。 <Polymerization inhibitor>
There is no limitation in particular in a polymerization inhibitor, A well-known polymerization inhibitor can be used. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, monoesterified hydroquinone, N-nitrosodiphenylamine, phenothiazine, 4-t-butylcatechol, N-phenylnaphthylamine, 2,6-di-t-butyl-p- Methylphenol, 2,5-di-t-butylhydroquinone, 1,4-benzoquinone, 2,6-di-t-butyl-1,4-benzoquinone, methyl-p-benzoquinone, 2,5-diphenyl-p- Examples include benzoquinone, 4-methoxyphenol, chloranil, pyrogallol, 2-oxydiphenylamine, and phenothiazine.
　市販の重合禁止剤としては、例えば、キノパワーＱＳ－１０、キノパワーＱＳ－２０、キノパワーＱＳ－３０、キノパワーＱＳ－４０、キノパワーＱＳ－Ｗ１０（川崎化成工業社製）、メトキノンフレーク、ノンフレックスアルバ、ＭＨ、ＴＢＨ、ＰＢＱ、トルキノン、ＴＢＱ（精工化学社製）等が挙げられる。 Examples of commercially available polymerization inhibitors include Kinopower QS-10, Kinopower QS-20, Kinopower QS-30, Kinopower QS-40, Kinopower QS-W10 (manufactured by Kawasaki Kasei Kogyo Co., Ltd.), Metoquinone Flakes, Nonflex Alba, MH, TBH, PBQ, tolquinone, TBQ (manufactured by Seiko Chemical Co., Ltd.) and the like can be mentioned.
　重合禁止剤は、分散液の保存安定性を高め、硬化性を確保する作用を有する。このような作用等を考慮して、分散液中の重合禁止剤の量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．００５～０．４重量部、より好ましくは０．０１～０．４重量部、より一層好ましくは０．０１～０．３重量部、さらに好ましくは０．０２～０．３重量部、さらに一層好ましくは０．０２～０．２重量部、特に好ましくは０．０３５～０．２重量部である。重合禁止剤としては、液状の重合性基を有する化合物に溶解する重合禁止剤が好ましい。 The polymerization inhibitor has the effect of increasing the storage stability of the dispersion and ensuring curability. In consideration of such actions and the like, the amount of the polymerization inhibitor in the dispersion is preferably 0.005 to 0.4 weight with respect to 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Parts, more preferably 0.01 to 0.4 parts by weight, even more preferably 0.01 to 0.3 parts by weight, still more preferably 0.02 to 0.3 parts by weight, still more preferably 0.02 to The amount is 0.2 parts by weight, particularly preferably 0.035 to 0.2 parts by weight. As the polymerization inhibitor, a polymerization inhibitor that is soluble in a compound having a liquid polymerizable group is preferable.
＜界面活性剤＞
　界面活性剤は、乳化剤として作用するものが好ましい。界面活性剤としては、例えば、カチオン性、アニオン性、両性またはノニオン性の界面活性剤が挙げられ、好ましくは、アニオン性またはノニオン性の界面活性剤である。界面活性剤は、単独で用いてもよく、２種以上を組み合わせても用いてもよい。 <Surfactant>
The surfactant preferably acts as an emulsifier. Examples of the surfactant include a cationic, anionic, amphoteric or nonionic surfactant, and an anionic or nonionic surfactant is preferable. Surfactants may be used alone or in combination of two or more.
　アニオン性界面活性剤としては、例えば、パルミチン酸ナトリウム等の脂肪酸ナトリウム、ポリオキシエチレンラウリルエーテルカルボン酸ナトリウム等のエーテルカルボン酸ナトリウム、ラウロイルサルコシンナトリウム、Ｎ－ラウロイルグルタミン酸ナトリウム等の高級脂肪酸のアミノ酸縮合物、高級アルキルスルホン酸塩、ラウリン酸エステルスルホン酸塩等の高級脂肪酸エステルスルホン酸塩、ジオクチルスルホサクシネート等のジアルキルスルホコハク酸塩、オレイン酸アミドスルホン酸等の高級脂肪酸アミドスルホン酸塩、ドデシルベンゼンスルホン酸ナトリウム、ジイソプロピルナフタレンスルホン酸塩等のアルキルアリールスルホン酸塩、アルキルアリールスルホン酸塩のホルマリン縮合物、ペンタデカン－２－サルフェート等の高級アルコール硫酸エステル塩、ジポリオキシエチレンドデシルエーテルリン酸エステル等のポリオキシエチレンアルキルリン酸エステル、リグニンスルホン酸塩、ポリオキシエチレン－１－（アリルオキシメチル）アルキルエーテル硫酸アンモニウム、ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸アンモニウム、ビス（ポリオキシエチレン多環フェニルエーテル）ビスメタクリレート硫酸エステル塩、アルキルアリルサクシネートスルホン酸ナトリウム塩、ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム、２－ソジウムスルホエチルメタクリレート、アルコキシポリエチレングリコールマレイン酸エステル、高級アルコールの硫酸エステル塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩およびビニルスルホサクシネート、ポリ（メタ）アクリル酸ナトリウム、ポリ（メタ）アクリル酸アンモニウム、（メタ）アクリル酸－（メタ）アクリル酸エステル共重合体、スチレンーマレイン酸共重合体、スチレンーマレイン酸共重合体アンモニウム塩、スチレンーマレイン酸ハーフエステル共重合体アンモニウム塩、カルボキシメチルセルロースナトリウムおよびナフタレンスルホン酸ナトリウムホルマリン縮合物等が挙げられる。 Examples of the anionic surfactant include fatty acid sodium such as sodium palmitate, sodium ether carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, amino acid condensate of higher fatty acid such as sodium lauroyl sarcosine, sodium N-lauroyl glutamate, etc. Higher fatty acid ester sulfonates such as higher alkyl sulfonates and lauric acid ester sulfonates, dialkyl sulfosuccinates such as dioctyl sulfosuccinate, higher fatty acid amide sulfonates such as oleic acid amide sulfonic acid, dodecylbenzene sulfone Acid aryl, alkylaryl sulfonates such as diisopropylnaphthalene sulfonate, formalin condensates of alkyl aryl sulfonate, pentadecane-2-sulfate Higher alcohol sulfates such as dipolyoxyethylene dodecyl ether phosphates, polyoxyethylene alkyl phosphates such as lignin sulfonate, polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate, polyoxy Ethylene nonylpropenyl phenyl ether ammonium sulfate, bis (polyoxyethylene polycyclic phenyl ether) bismethacrylate sulfate ester, alkylallyl succinate sulfonate sodium salt, polyoxyalkylene alkenyl ether ammonium sulfate, 2-sodium sulfoethyl methacrylate, alkoxy polyethylene glycol Maleate ester, sulfate ester of higher alcohol, higher carboxylate, alkylbenzene sulfonate, poly Xylethylene alkyl sulfate salt, polyoxyethylene alkyl phenyl ether sulfate salt and vinyl sulfosuccinate, sodium poly (meth) acrylate, ammonium poly (meth) acrylate, (meth) acrylic acid- (meth) acrylic acid ester copolymer Examples thereof include styrene-maleic acid copolymer, styrene-maleic acid copolymer ammonium salt, styrene-maleic acid half ester copolymer ammonium salt, sodium carboxymethylcellulose and sodium naphthalene sulfonate formalin condensate.
　カチオン性界面活性剤としては、例えば、ドデシルアミン塩酸塩等のアルキルアミン塩酸塩、アルキルジメチルベンジルアンモニウム塩、アルキルイソキノリニウム塩、ジアルキルモルホリニウム塩等のアルキル四級アンモニウム塩、塩化ベンゼトニウム、およびポリアルキルビニルピリジニウム塩、ドデシルトリメチルアンモニウム塩およびセチルトリメチルアンモニウム塩等のアルキルアンモニウム塩、セチルピリジウム塩およびデシルピリジウム塩等のアルキルピリジウム塩、オキシアルキレントリアルキルアンモニウム塩、ジオキシアルキレンジアルキルアンモニウム塩、アリルトリアルキルアンモニウム塩およびジアリルジアルキルアンモニウム塩、ポリジアリルジメチルアンモニウムクロライド等が挙げられる。 Examples of the cationic surfactant include alkylamine hydrochlorides such as dodecylamine hydrochloride, alkyl quaternary ammonium salts such as alkyldimethylbenzylammonium salt, alkylisoquinolinium salt and dialkylmorpholinium salt, benzethonium chloride, And polyalkylvinylpyridinium salts, alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkylammonium salt, Examples include allyltrialkylammonium salt, diallyldialkylammonium salt, and polydiallyldimethylammonium chloride.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンラノリンアルコール、ポリオキシエチレンアルキルフェノールホルマリン縮合物、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレングリセリルモノ脂肪酸エステル、ポリオキシプロピレングリコールモノ脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレンヒマシ油誘導体、ポリオキシエチレン脂肪酸エステル、高級脂肪酸グリセリンエステル、ソルビタン脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレン脂肪酸アミド、アルキロールアミド、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルカンジオール、アルコキシポリエチレングリコールメタクリレート、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレン脂肪酸アミド、ポリアルキレンポリアミンアルキレンオキシド付加物、ポリアルキレンポリイミンアルキレンオキシド付加物、ポリビニルピロリドン、ジシアンジアミドポリアルキレンポリアミン縮合物、ポリエチレングリコール、ポリビニルアルコール等が挙げられる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, polyoxyethylene alkylphenol formalin condensate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl mono fatty acid. Ester, polyoxypropylene glycol monofatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene castor oil derivative, polyoxyethylene fatty acid ester, higher fatty acid glycerin ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene Block polymer, polyoxyethylene fatty acid amide, alkylolamide, polyoxye Lenalkylamine, polyoxyethylene alkanediol, alkoxy polyethylene glycol methacrylate, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene fatty acid amide, polyalkylene polyamine alkylene oxide adduct, polyalkylene polyimine alkylene oxide adduct, Examples include polyvinyl pyrrolidone, dicyandiamide polyalkylene polyamine condensate, polyethylene glycol, polyvinyl alcohol and the like.
　両性界面活性剤としては、例えば、Ｎ－ラウリルアラニン、Ｎ，Ｎ，Ｎ－トリメチルアミノプロピオン酸、Ｎ，Ｎ，Ｎ－トリヒドロキシエチルアミノプロピオン酸、Ｎ－ヘキシル－Ｎ，Ｎ－ジメチルアミノ酢酸、１－（２－カルボキシエチル）ピリミジニウムベタイン、レシチン、ラウリルベタインおよびラウリルジメチルアミンオキサイド等が挙げられる。 Examples of amphoteric surfactants include N-laurylalanine, N, N, N-trimethylaminopropionic acid, N, N, N-trihydroxyethylaminopropionic acid, N-hexyl-N, N-dimethylaminoacetic acid, Examples thereof include 1- (2-carboxyethyl) pyrimidinium betaine, lecithin, lauryl betaine, and lauryl dimethylamine oxide.
　市販品の界面活性剤としては、例えば、エマール０、エマール１０Ｇ、エマール２Ｆペースト、エマール２０Ｃ、エマールＥ－２７Ｃ、エマール２７０J、エマールＥ－２７Ｃ、ネオペレックスＧＳ、ネオペレックスＧ－１５、ネオペレックスＧ－２５、ネオペレックスＧ－６５、ラテムルＰＤ－１０４、ペレックスＯＴ－Ｐ、ペレックスＴＲ、ペレックスＳＳ－Ｌ、ペレックスＳＳ－Ｈ、デモールＮ、デモールＥＰ、エマルゲン１０２ＫＧ、エマルゲン１０４Ｐ、エマルゲン１０５、エマルゲン１０６、エマルゲン１０８、エマルゲン４０４、エマルゲン１３０Ｋ、エマルゲン１４７、エマルゲンＬＳ－１０６、エマルゲンＬＳ－１１０、エマルゲンＡ－６０、エマルゲン１０９Ｐ、エマルゲン３５０、ラテムルＰＤ－４２０、レオドール４３０Ｖ、エマノーン１１１２、エマノーンＣＨ－２５、アミート１０２、アセタミン８６、コータミン２４Ｐ、アンヒトール２４Ｂ、ネオペレックスＮｏ．６パウダー、ラテムルＥ－１０００Ａ、ペレックスＯＴ－Ｐ、エマルゲンＬＳ－１１４、エマルゲン２１０Ｐ、エマルゲン２２０、エマルゲン３０６Ｐ、エマルゲン３２０Ｐ、エマルゲン４０８、エマルゲン４０９ＰＶ、エマルゲン４２０、アンヒトール８６Ｂおよびアンヒトール２０ＢＳ（花王社製）、ノイゲンＥＡ－１７７、ノイゲンＸＬ－４０、ノイゲンＴＤＳ－３０、ノイゲンＴＤＸ－８０、ノイゲンＬＰ－８０、ＤＫＳ　ＮＬ－１５、ＤＫＳ　ＮＬ－５０、ＤＫＳ　ＮＬ－８０、ＤＫＳ　ＮＬ－１１０、ＤＫＳ　ＮＬ－１８０、ノイゲンＴＤＳ－７０、ノイゲンＴＤＳ－１００、ノイゲンＥＴ－８３、ノイゲンＥＴ－１６０、ノイゲンＹＸ－４００、ハイテノールＮＦ－０８、ハイテノール２２７Ｌ、プライサーフＡ２１２Ｃ、プライサーフＡ２１０Ｄ、ネオコールＰ、モノゲンＹ－１００、カチオーゲンＴＭＬ、アクアロンＫＨ－１０、アクアロンＫＨ－１０２５、アクアロンＨＳ－１０、アクアロンＲＮ－２０、アクアロンＲＮ－３０、ピッツコールＫ－１７ＬおよびピッツコールＶ－７１５４（第一工業製薬社製）、アデカプルロニックＦ１０８、アデカプルロニックＬ－６１、アデカプルロニック１７Ｒ－２（ＡＤＥＫＡ社製）エレミノールＪＳ－２０、エレミノールＲＳ－３０００、サンモリンＯＴ－７０およびキャリボンＥＮ―２００（三洋化成工業社製）、クラレポバールＰＶＡ－１０３、クラレポバールＰＶＡ－１０５、クラレポバールＰＶＡ－１１７、クラレポバールＰＶＡ－２１７、クラレポバールＰＶＡ－２０５、クラレポバールＰＶＡ－２０３、クラレポバールＰＶＡ－２１０、クラレポバールＰＶＡ－２３５、クラレポバールＰＶＡ－４０３、クラレポバールＰＶＡ－４０５、クラレポバールＰＶＡ－４１７、クラレポバールＭ－２０５、クラレポバールＭＰ－２０３、クラレポバールＫＬ－５０６およびクラレポバールＫＬ－３１８（クラレ社製）、アクマリムＡＫＭ－１５１１－６０、アクマリムＡＫＭ－０５３１、ポリスターＯＭおよびプロノン♯１０２（日油社製）等が挙げられる。 Examples of commercially available surfactants include EMAL 0, EMAL 10G, EMAL 2F paste, EMAL 20C, EMAL E-27C, EMAL 270J, EMAL E-27C, Neoperex GS, Neoperex G-15, Neoperex G -25, Neoperex G-65, Latemul PD-104, Perex OT-P, Perex TR, Perex SS-L, Perex SS-H, Demol N, Demal EP, Emulgen 102KG, Emulgen 104P, Emulgen 105, Emalgen 106, Emulgen 108, Emulgen 404, Emulgen 130K, Emulgen 147, Emulgen LS-106, Emulgen LS-110, Emulgen A-60, Emulgen 109P, Emulgen 350, Latemul PD-420, Rheodor 430V, Emanon 1112, Emanon CH-25, Amit 102, Acetamine 86, Coatamine 24P, Amhitor 24B, Neoperex No. 6 powder, Latemul E-1000A, Perex OT-P, Emulgen LS-114, Emulgen 210P, Emulgen 220, Emulgen 306P, Emulgen 320P, Emulgen 408, Emulgen 409PV, Emulgen 420, Amphital 86B and Amphital 20BS (manufactured by Kao Corporation), Neugen EA-177, Neugen XL-40, Neugen TDS-30, Neugen TDX-80, Neugen LP-80, DKS NL-15, DKS NL-50, DKS NL-80, DKS NL-110, DKS NL-180, Neugen TDS-70, Neugen TDS-100, Neugen ET-83, Neugen ET-160, Neugen YX-400, Haitenol NF-08, Haitenol 227L, Prisurf A212C, Isafu A210D, Neocor P, Monogen Y-100, Catiogen TML, Aqualon KH-10, Aqualon KH-1025, Aqualon HS-10, Aqualon RN-20, Aqualon RN-30, Pitzkor K-17L and Pitzkor V-7154 (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Pluronic F108, Adeka Pluronic L-61, Adeka Pluronic 17R-2 (manufactured by ADEKA), Eleminol JS-20, Eleminol RS-3000, Sanmorin OT-70, and Caribon EN-200 (Sanyo) Manufactured by Kasei Kogyo Co., Ltd.), Kuraray Poval PVA-103, Kuraray Poval PVA-105, Kuraray Poval PVA-117, Kuraray Poval PVA-217, Kuraray Poval PVA-205, Kuraray Poval PVA-203 Kuraraypoval PVA-210, Kuraraypoval PVA-235, Kuraraypoval PVA-403, Kuraraypoval PVA-405, Kuraraypoval PVA-417, Kuraraypoval M-205, Kuraraypoval MP-203, Kuraraypoval KL-506 and Kuraraypoval Examples thereof include KL-318 (manufactured by Kuraray Co., Ltd.), Akumarim AKM-1511-60, Akumarim AKM-0531, Polystar OM, and Pronon # 102 (manufactured by NOF Corporation).
　本発明の分散液は、好ましくは界面活性剤を含む。本発明の分散液が界面活性剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは１重量部以上であり、好ましくは３０重量部以下、より好ましくは１５重量部以下、さらに好ましくは１０重量部以下である。 The dispersion of the present invention preferably contains a surfactant. When the dispersion of the present invention contains a surfactant, the amount thereof is preferably 1 part by weight or more, preferably 30 parts by weight, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. Below, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.
＜光重合開始剤＞
　光重合開始剤とは、光の作用により活性種を生じる化合物である。光重合開始剤としては、例えば、光の作用により活性ラジカルを発生する光ラジカル発生剤、光の作用により酸を発生する光酸発生剤および光の作用により塩基を発生する光塩基発生剤が挙げられる。 <Photopolymerization initiator>
The photopolymerization initiator is a compound that generates active species by the action of light. Examples of the photopolymerization initiator include a photo radical generator that generates an active radical by the action of light, a photo acid generator that generates an acid by the action of light, and a photo base generator that generates a base by the action of light. It is done.
　光ラジカル発生剤としては、例えば、ベンゾイン化合物、ベンゾフェノン化合物、アルキルフェノン化合物、アシルホスフィンオキサイド化合物、トリアジン化合物、スルホン酸誘導体、オニウム塩類（ヨードニウム塩およびスルホニウム塩等）、カルボン酸エステル類等が挙げられる。 Examples of the photo radical generator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, sulfonic acid derivatives, onium salts (such as iodonium salts and sulfonium salts), and carboxylic acid esters. .
　ベンゾイン化合物としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテルおよびベンゾインイソブチルエーテル等が挙げられる。 Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
　ベンゾフェノン化合物としては、例えば、ベンゾフェノン、４－メチルベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、３，３’，４，４’－テトラ（ｔｅｒｔ－ブチルパーオキシカルボニル）ベンゾフェノンおよび２，４，６－トリメチルベンゾフェノン等が挙げられる。 Examples of the benzophenone compound include benzophenone, 4-methylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert -Butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.
　アルキルフェノン化合物としては、例えば、ジエトキシアセトフェノン、２－メチル－２－モルホリノ－１－（４－メチルチオフェニル）プロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１，２－ジフェニル－２，２－ジメトキシエタン－１－オン、２－ヒドロキシ－２－メチル－１－〔４－（２－ヒドロキシエトキシ）フェニル〕プロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチルプロピオフェノンおよび２－ヒドロキシ－２－メチル－１－〔４－（１－メチルビニル）フェニル〕プロパン－１－オンのオリゴマー等が挙げられる。 Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl-1 -[4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone and 2-hydroxy-2-methyl-1- [4- ( And oligomers of 1-methylvinyl) phenyl] propan-1-one.
　アシルホスフィンオキサイド化合物としては、例えば、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイドおよびビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド等が挙げられる。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
　トリアジン化合物としては、例えば、２，４－ビス（トリクロロメチル）－６－（４－メトキシフェニル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシナフチル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－（４－メトキシスチリル）－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（５－メチルフラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（フラン－２－イル）エテニル〕－１，３，５－トリアジン、２，４－ビス（トリクロロメチル）－６－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－１，３，５－トリアジンおよび２，４－ビス（トリクロロメチル）－６－〔２－（３，４－ジメトキシフェニル）エテニル〕－１，３，５－トリアジン等が挙げられる。 Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloro Methyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.
　光ラジカル発生剤としては、市販のものを用いることができる。市販の光ラジカル発生剤としては、例えば、イルガキュア（Ｉｒｇａｃｕｒｅ）（登録商標）１１７３、９０７、１８４、６５１、８１９、２５０、２９５９、１２７、７５４および３６９（ＢＡＳＦジャパン（株））、セイクオール（登録商標）ＢＺ、ＺおよびＢＥＥ（精工化学（株））、カヤキュアー（ｋａｙａｃｕｒｅ）（登録商標）ＢＰ１００（日本化薬（株））、カヤキュアーＵＶＩ－６９９２（ダウ社製）、アデカオプトマーＳＰ－１５２およびＳＰ－１７０（（株）ＡＤＥＫＡ）、ＴＡＺ－ＡおよびＴＡＺ－ＰＰ（日本シイベルヘグナー（株））、ＴＡＺ－１０４（（株）三和ケミカル）およびＭＢＦ（ＢＡＳＦジャパン（株））等が挙げられる。これら光ラジカル発生剤は、単独で使用してもよく、組み合わせて使用してもよい。組み合わせの具体例としては、イルガキュア（登録商標）５００（１－ヒドロキシ－シクロヘキシル－フェニル－ケトン／ベンゾフェノン：５０／５０％）、イルガキュア（登録商標）１７００（ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド／２－ヒドロキシ－２－メチルフェニルプロパン－１－オン：２５／７５％）およびイルガキュア（登録商標）１８００（ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド／１－ヒドロキシシクロヘキシル－フェニルケトン：２５／７５％）（ＢＡＳＦジャパン（株））等が挙げられる。 Commercially available photo radical generators can be used. Examples of commercially available photoradical generators include Irgacure (registered trademark) 1173, 907, 184, 651, 819, 250, 2959, 127, 754 and 369 (BASF Japan Co., Ltd.), Sequol (registered trademark). ) BZ, Z and BEE (Seiko Chemical Co., Ltd.), Kayacure (registered trademark) BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adekaoptomer SP-152 and SP -170 (ADEKA Corporation), TAZ-A and TAZ-PP (Nippon Siebel Hegner Corporation), TAZ-104 (Sanwa Chemical Co., Ltd.) and MBF (BASF Japan Corporation). These photo radical generators may be used alone or in combination. Specific examples of the combination include Irgacure (registered trademark) 500 (1-hydroxy-cyclohexyl-phenyl-ketone / benzophenone: 50/50%), Irgacure (registered trademark) 1700 (bis (2,6-dimethoxybenzoyl) -2 , 4,4-trimethylpentylphosphine oxide / 2-hydroxy-2-methylphenylpropan-1-one: 25/75%) and Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide / 1-hydroxycyclohexyl-phenylketone: 25/75%) (BASF Japan Ltd.).
　光酸発生剤としては、例えば、スルホン酸誘導体、オニウム塩類、ジカルボン酸イミド類等が挙げられる。 Examples of the photoacid generator include sulfonic acid derivatives, onium salts, dicarboxylic imides, and the like.
　スルホン酸誘導体としては、例えば、ジスルホン類、ジスルホニルジアゾメタン類、ジスルホニルメタン類、スルホニルベンゾイルメタン類、トリフルオロメチルスルホネート類、ベンゾインスルホネート類、１－オキシ－２－ヒドロキシ－３－プロピルアルコールのスルホネート類、ピロガロールトリスルホネート類、ベンジルスルホネート類が挙げられる。具体的には、ジフェニルジスルホン、ジトシルジスルホン、ビス（フェニルスルホニル）ジアゾメタン、ビス（クロルフェニルスルホニル）ジアゾメタン、ビス（キシリルスルホニル）ジアゾメタン、フェニルスルホニルベンゾイルジアゾメタン、ビス（シクロヘキシルスルホニル）メタン、ベンゾイントシラート、１、２－ジフェニル－２－ヒドロキシプロピルトシラート、１、２－ジ（４－メチルメルカプトフェニル）－２－ヒドロキシプロピルトシラート、ピロガロールメチルスルホネート、ピロガロールエチルスルホネート、２，６－ジニトロフェニルメチルトシラート、オルト－ニトロフェニルメチルトシラート、パラ－ニトロフェニルトシラート等が挙げられる。 Examples of the sulfonic acid derivatives include disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, trifluoromethylsulfonates, benzoinsulfonates, and sulfonates of 1-oxy-2-hydroxy-3-propyl alcohol. , Pyrogallol trisulfonates, benzyl sulfonates. Specifically, diphenyl disulfone, ditosyl disulfone, bis (phenylsulfonyl) diazomethane, bis (chlorophenylsulfonyl) diazomethane, bis (xylylsulfonyl) diazomethane, phenylsulfonylbenzoyldiazomethane, bis (cyclohexylsulfonyl) methane, benzoin tosylate 1,2-diphenyl-2-hydroxypropyl tosylate, 1,2-di (4-methylmercaptophenyl) -2-hydroxypropyl tosylate, pyrogallol methyl sulfonate, pyrogallol ethyl sulfonate, 2,6-dinitrophenyl methyl tosylate And lato, ortho-nitrophenyl methyl tosylate, para-nitrophenyl tosylate and the like.
　オニウム塩類としては、例えば、テトラフルオロボレート（ＢＦ４－）、ヘキサフルオロホスフェート（ＰＦ６－）、ヘキサフルオロアンチモネート（ＳｂＦ６－）、ヘキサフルオロアルセネート（ＡｓＦ６－）、ヘキサクロルアンチモネート（ＳｂＣｌ６－）、テトラフェニルボレート、テトラキス（トリフルオロメチルフェニル）ボレート、テトラキス（ペンタフルオロメチルフェニル）ボレート、過塩素酸イオン（ＣｌＯ４－）、トリフルオロメタンスルホン酸イオン（ＣＦ３ＳＯ３－）、フルオロスルホン酸イオン（ＦＳＯ３－）、トルエンスルホン酸イオン、トリニトロベンゼンスルホン酸アニオン、トリニトロトルエンスルホン酸アニオン等のアニオンを有するスルホニウム塩およびヨードニウム塩等が挙げられる。 Examples of onium salts include tetrafluoroborate (BF 4− ), hexafluorophosphate (PF 6− ), hexafluoroantimonate (SbF 6− ), hexafluoroarsenate (AsF 6− ), hexachloroantimonate ( SbCl 6− ), tetraphenylborate, tetrakis (trifluoromethylphenyl) borate, tetrakis (pentafluoromethylphenyl) borate, perchlorate ion (ClO 4− ), trifluoromethanesulfonate ion (CF 3 SO 3− ), fluorosulfonic acid ion (FSO 3-), include toluenesulfonate ion, trinitrobenzene sulfonate anion, a sulfonium salt and iodonium salts having an anion such as trinitrotoluene sulfonate anion
　スルホニウム塩としては、例えば、トリフェニルスルホニウムヘキサフルオロアシルネート、トリフェニルスルホニウムヘキサフルオロボレート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオベンジル）ボレート、メチルジフェニルスルホニウムテトラフルオロボレート、メチルジフェニルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、ジメチルフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、ジフェニルナフチルスルホニウムヘキサフルオロアルセネート、トリトイルスルホニウムヘキサフルオロホスフェート、アニシルジフェニルスルホニウムヘキサヘキサフルオルアンチモネート、４－ブトキシフェニルジフェニルスルホニウムテトラフルオロボレート、４－ブトキシフェニルジフェニルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、４－クロロフェニルジフェニルスルホニウムヘキサフルオロアンチモネート、トリス（４－フェノキシフェニル）スルホニウムヘキサフルオロホスフェート、ジ（４－エトキシフェニル）メチルスルホニウムヘキサフルオロアルセネート、４－アセチルフェニルジフェニルスルホニウムテトラフルオロボレート、４－アセチルフェニルジフェニルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、トリス（４－チオメトキシフェニル）スルホニウムヘキサフルオロホスフェート、ジ（メトキシスルホニルフェニル）メチルスルホニウムヘキサフルオロアンチモネート、ジ（メトキシナフチル）メチルスルホニウムテトラフルオロボレート、ジ（メトキシナフチル）メチルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、ジ（カルボメトキシフェニル）メチルスルホニウムヘキサフルオロホスフェート、（４－オクチルオキシフェニル）ジフェニルスルホニウムテトラキス（３，５－ビス－トリフルオロメチルフェニル）ボレート、トリス（ドデシルフェニル）スルホニウムテトラキス（３，５－ビス－トリフルオロメチルフェニル）ボレート、４－アセトアミドフェニルジフェニルスルホニウムテトラフルオロボレート、４－アセトアミドフェニルジフェニルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、ジメチルナフチルスルホニウムヘキサフルオロホスフェート、トリフルオロメチルジフェニルスルホニウムテトラフルオロボレート、トリフルオロメチルジフェニルスルホニウムテトラキス（ペンタフルオロベンジル）ボレート、フェニルメチルベンジルスルホニウムヘキサフルオロホスフェート、１０－メチルフェノキサチイニウムヘキサフルオロホスフェート、５－メチルチアントレニウムヘキサフルオロホスフェート、１０－フェニル－９，９－ジメチルチオキサンテニウムヘキサフルオロホスフェート、１０－フェニル－９－オキソチオキサンテニウムキサンテニウムテトラフルオロボレート、１０－フェニル－９－オキソチオキサンテニウムテトラキス（ペンタフルオロベンジル）ボレート、５－メチル－１０－オキソチアトレニウムテトラフルオロボレート、５－メチル－１０－オキソチアトレニウムテトラキス（ペンタフルオロベンジル）ボレート、および５－メチル－１０，１０－ジオキソチアトレニウムヘキサフルオロホスフェート等が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium hexafluoroacylate, triphenylsulfonium hexafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorobenzyl) borate, methyldiphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium. Tetrakis (pentafluorobenzyl) borate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritoylsulfonium hexafluorophosphate, anisyldiphenyls Honium hexahexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-butoxyphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, tris (4-phenoxyphenyl) Sulfonium hexafluorophosphate, di (4-ethoxyphenyl) methylsulfonium hexafluoroarsenate, 4-acetylphenyldiphenylsulfonium tetrafluoroborate, 4-acetylphenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, tris (4-thiomethoxyphenyl) ) Sulfonium hexafluorophosphate, di (methoxysulfonyl) Nyl) methylsulfonium hexafluoroantimonate, di (methoxynaphthyl) methylsulfonium tetrafluoroborate, di (methoxynaphthyl) methylsulfonium tetrakis (pentafluorobenzyl) borate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, (4- Octyloxyphenyl) diphenylsulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, tris (dodecylphenyl) sulfonium tetrakis (3,5-bis-trifluoromethylphenyl) borate, 4-acetamidophenyldiphenylsulfonium tetrafluoro Borate, 4-acetamidophenyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, dimethyl Naphtylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, trifluoromethyldiphenylsulfonium tetrakis (pentafluorobenzyl) borate, phenylmethylbenzylsulfonium hexafluorophosphate, 10-methylphenoxathinium hexafluorophosphate, 5-methyl Thianthrenium hexafluorophosphate, 10-phenyl-9,9-dimethylthioxanthenium hexafluorophosphate, 10-phenyl-9-oxothioxanthenium xanthenium tetrafluoroborate, 10-phenyl-9-oxothioki Santenium tetrakis (pentafluorobenzyl) borate, 5-methyl-10-oxothiatrenium teto Tetrafluoroborate, 5-methyl-10-oxo-thia Torre tetrakis (pentafluorobenzyl) borate, and 5-methyl-10,10-dioxo-thia tray hexafluorophosphate, and the like.
　ヨードニウム塩としては、例えば、（４－ｎ－デシロキシフェニル）フェニルヨードニウムヘキサフルオロアンチモネート、〔４－（２－ヒドロキシ－ｎ－テトラデシロキシ）フェニル〕フェニルヨードニウムヘキサフルオロアンチモネート、〔４－（２－ヒドロキシ－ｎ－テトラデシロキシ）フェニル〕フェニルヨードニウムトリフルオロスルホネート、〔４－（２－ヒドロキシ－ｎ－テトラデシロキシ）フェニル〕フェニルヨードニウムヘキサフルオロホスフェート、〔４－（２－ヒドロキシ－ｎ－テトラデシロキシ）フェニル〕フェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－ｔ－ブチルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（４－ｔ－ブチルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（４－ｔ－ブチルフェニル）ヨードニウムトリフルオロスルホネート、ビス（４－ｔ－ブチルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ビス（ドデシルフェニル）ヨードニウムテトラフルオロボレート、ビス（ドデシルフェニル）ヨードニウムヘキサフルオロホスフェート、ビス（ドデシルフェニル）ヨードニウムトリフルオロメチルスルフォネート、ジ（ドデシルフェニル）ヨードニウムヘキサフルオロアンチモネート、ジ（ドデシルフェニル）ヨードニウムトリフラート、ジフェニルヨードニウムビスルフェート、４，４’－ジクロロジフェニルヨードニウムビスルフェート、４，４’－ジブロモジフェニルヨードニウムビスルフェート、３，３’－ジニトロジフェニルヨードニウムビスルフェート、４，４’－ジメチルジフェニルヨードニウムビスルフェート、４，４’－ビススクシンイミドジフェニルヨードニウムビスルフェート、３－ニトロジフェニルヨードニウムビスルフェート、４，４’－ジメトキシジフェニルヨードニウムビスルフェート、ビス（ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、（４－オクチルオキシフェニル）フェニルヨードニウムテトラキス（３，５－ビス－トリフルオロメチルフェニル）ボレート等が挙げられる。 Examples of the iodonium salt include (4-n-decyloxyphenyl) phenyliodonium hexafluoroantimonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate, [4- ( 2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium trifluorosulfonate, [4- (2-hydroxy-n-tetradecyloxy) phenyl] phenyliodonium hexafluorophosphate, [4- (2-hydroxy-n- Tetradecyloxy) phenyl] phenyliodonium tetrakis (pentafluorophenyl) borate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, bis (4-t-butylphenyl) iodonium hex Fluorophosphate, bis (4-tert-butylphenyl) iodonium trifluorosulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoro Borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium trifluoromethylsulfonate, di (dodecylphenyl) iodonium hexafluoroantimonate, di (dodecylphenyl) iodonium triflate, diphenyliodonium bissulfate, 4 , 4'-dichlorodiphenyliodonium bisulphate, 4,4'-dibromodiphenyliodonium biphenyl Rufate, 3,3'-dinitrodiphenyliodonium bisulphate, 4,4'-dimethyldiphenyliodonium bisulphate, 4,4'-bissuccinimide diphenyliodonium bisulphate, 3-nitrodiphenyliodonium bisulphate, 4,4'-dimethoxy Examples thereof include diphenyliodonium bisulphate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (4-octyloxyphenyl) phenyliodonium tetrakis (3,5-bis-trifluoromethylphenyl) borate.
　その他のオニウム塩としては、例えば、ｐ－メトキシベンゼンジアゾニウム・ヘキサフルオロアンチモネート等の芳香族ジアゾニウム塩が挙げられる。 Examples of other onium salts include aromatic diazonium salts such as p-methoxybenzenediazonium and hexafluoroantimonate.
　商業的に入手できるオニウム塩としては、例えば、サンエイドＳＩ－６０、ＳＩ－８０、ＳＩ－１００、ＳＩ－６０Ｌ、ＳＩ－８０Ｌ、ＳＩ－１００Ｌ、ＳＩ－Ｌ１４５、ＳＩ－Ｌ１５０、ＳＩ－Ｌ１６０、ＳＩ－Ｌ１１０、ＳＩ－Ｌ１４７（以上、三新化学工業社製）、ＵＶＩ－６９５０、ＵＶＩ－６９７０、ＵＶＩ－６９７４、ＵＶＩ－６９９０（以上、ユニオンカーバイド社製）、アデカオプトマーＳＰ－１５０、ＳＰ－１５１、ＳＰ－１７０、ＳＰ－１７１、ＳＰ－１７２（以上、ＡＤＥＫＡ社製）、Ｉｒｇａｃｕｒｅ　２６１、Ｉｒｇａｃｕｒｅ２５０（ＢＡＳＦ社製）、ＣＩ－２４８１、ＣＩ－２６２４、ＣＩ－２６３９、ＣＩ－２０６４（以上、日本曹達社製）、ＣＤ－１０１０、ＣＤ－１０１１、ＣＤ－１０１２（以上、サートマー社製）、ＤＳ－１００、ＤＳ－１０１、ＤＡＭ－１０１、ＤＡＭ－１０２、ＤＡＭ－１０５、ＤＡＭ－２０１、ＤＳＭ－３０１、ＮＡＩ－１００、ＮＡＩ－１０１、ＮＡＩ－１０５、ＮＡＩ－１０６、ＳＩ－１００、ＳＩ－１０１、ＳＩ－１０５、ＳＩ－１０６、ＰＩ－１０５、ＮＤＩ－１０５、ＢＥＮＺＯＩＮ　ＴＯＳＹＬＡＴＥ、ＭＢＺ－１０１、ＭＢＺ－３０１、ＰＹＲ－１００、ＰＹＲ－２００、ＤＮＢ－１０１、ＮＢ－１０１、ＮＢ－２０１、ＢＢＩ－１０１、ＢＢＩ－１０２、ＢＢＩ－１０３、ＢＢＩ－１０９（以上、みどり化学社製）、ＰＣＩ－０６１Ｔ、ＰＣＩ－０６２Ｔ、ＰＣＩ－０２０Ｔ、ＰＣＩ－０２２Ｔ（以上、日本化薬社製）、ＩＢＰＦ、ＩＢＣＦ（三和ケミカル社製）ＣＤ１０１２（サートマー社製）、ＩＢＰＦ、ＩＢＣＦ（以上、三和ケミカル社製）、ＢＢＩ－１０１、ＢＢＩ－１０２、ＢＢＩ－１０３、ＢＢＩ－１０９（以上、みどり化学社製）、ＵＶＥ１０１４（ゼネラルエレクトロニクス社製）、ＲＨＯＤＯＲＳＩＬ－ＰＩ２０７４（ローディア社製）、ＷＰＩ－１１３、ＷＰＩ－１１６（和光純薬社製）等が挙げられる。 Commercially available onium salts include, for example, Sun Aid SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-L145, SI-L150, SI-L160, SI -L110, SI-L147 (above, Sanshin Chemical Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, Union Carbide), Adekaoptomer SP-150, SP- 151, SP-170, SP-171, SP-172 (above, manufactured by ADEKA), Irgacure 261, Irgacure 250 (made by BASF), CI-2481, CI-2624, CI-2638, CI-2064 (above, Japan) Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, DS-100, DS-101, DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI -100, SI-101, SI-105, SI-106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.) Manufactured), IBPF, IBCF (manufactured by Sanwa Chemical) CD1012 (manufactured by Sartomer) , IBPF, IBCF (manufactured by Sanwa Chemical Co., Ltd.), BBI-101, BBI-102, BBI-103, BBI-109 (manufactured by Midori Chemical Co., Ltd.), UVE1014 (manufactured by General Electronics Co., Ltd.), RHODORSIL-PI2074 ( Rhodia), WPI-113, WPI-116 (Wako Pure Chemical Industries), and the like.
　また、J. Polymer Science: Part A: polymer Chemistry, Vol.31, 1473-1482 (1993)、J. Polymer Science: Part A: polymer Chemistry, Vol.31, 1483-1491 (1993) において記述されている方法により製造できるジアリールヨードニウム塩を使用することもできる。これらは、単独で使用してもよく、２種以上を併用してもよい。 Also described in J. Polymer Science: Part A: polymer Chemistry, Vol.31, 1473-1482 (1993), J. Polymer Science: ciPart A: polymer Chemistry, Vol.31, 1483-1491 (1993) Diaryliodonium salts that can be produced by the method can also be used. These may be used alone or in combination of two or more.
　ジカルボン酸イミド類としては、例えば、Ｎ－（メチルスルホニルオキシ）ナフタレン－１，８－ジカルボキシイミド、Ｎ－（トシルオキシ）ナフタレン－１，８－ジカルボキシイミド、Ｎ－［（トリフルオロメチル）スルホニルオキシ］ナフタレン－１，８－ジカルボキシイミド、Ｎ－（カンファースルホニルオキシ）ナフタレン－１，８－ジカルボキシイミド、Ｎ－（フェニルスルホニルオキシ）スクシンイミド、Ｎ－（トシルオキシ）スクシンイミド、Ｎ－［（トリフルオロメチル）スルホニルオキシ］スクシンイミド、Ｎ－（カンファースルホニルオキシ）スクシンイミド、Ｎ－［（トリフルオロメチル）スルホニルオキシ］フタルイミド、Ｎ－［（トリフルオロメチル）スルホニルオキシ］－シス－５－ノルボルネン－エンド－２，３－ジカルボキシイミド等が挙げられる。 Examples of the dicarboxylic imides include N- (methylsulfonyloxy) naphthalene-1,8-dicarboximide, N- (tosyloxy) naphthalene-1,8-dicarboximide, N-[(trifluoromethyl) sulfonyl Oxy] naphthalene-1,8-dicarboximide, N- (camphorsulfonyloxy) naphthalene-1,8-dicarboximide, N- (phenylsulfonyloxy) succinimide, N- (tosyloxy) succinimide, N-[(tri Fluoromethyl) sulfonyloxy] succinimide, N- (camphorsulfonyloxy) succinimide, N-[(trifluoromethyl) sulfonyloxy] phthalimide, N-[(trifluoromethyl) sulfonyloxy] -cis-5-norbornene-endo- , 3-dicarboximide and the like.
　光塩基発生剤としては、例えば、非環状のアシルオキシイミノ化合物、非環状のカルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α－アミノアセトフェノン誘導体化合物、４級アンモニウム塩誘導体化合物、α－ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物等が挙げられる。これらは、単独で使用してもよく、２種以上を併用してもよい。 Examples of photobase generators include acyclic acyloxyimino compounds, acyclic carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, Examples include sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, α-lactone ring derivative compounds, amine imide compounds, and phthalimide derivative compounds. These may be used alone or in combination of two or more.
　本発明の分散液が光重合開始剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、安定性、反応性および臭気の観点から、好ましくは０．０１重量部以上であり、好ましくは４０重量部以下、より好ましくは２０重量部以下、さらに好ましくは１０重量部以下、より一層好ましくは５重量部以下である。 When the dispersion of the present invention contains a photopolymerization initiator, the amount thereof is preferably from the viewpoint of stability, reactivity, and odor with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. The amount is 0.01 parts by weight or more, preferably 40 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
＜光安定剤＞
　光安定剤としては、例えば、紫外線吸収剤およびヒンダードアミン系光安定剤が挙げられる。光安定剤は単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <Light stabilizer>
Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. A light stabilizer may be used independently and may be used in combination of 2 or more type.
　紫外線吸収剤としては、例えば、サリチル酸類（例えば、例えば、フェニルサリシレート、ｐ－ｔ－ブチルフェニルサリシレート、ｐ－オクチルフェニルサリシレート等）、ベンゾフェノン類（例えば、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノン、２－ヒドロキシ－４－ドデシルオキシベンゾフェノン、２，２’－ジヒドロキシ－４－メトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－５－スルホベンゾフェノン等）、ベンゾトリアゾール類（例えば、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジｔｅｒｔ－アミルフェニル）ベンゾトリアゾール、２－｛（２’－ヒドロキシ－３’，３”，４”，５”，６”－テトラヒドロフタルイミドメチル）－５’－メチルフェニル｝ベンゾトリアゾール等）、トリアジン類（例えば、２，４，６－トリス（２－ヒドロキシ－４－オクチルオキシフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－オクチルオキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－［２，４－ジヒドロキシフェニル－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２，４－ビス（２－ヒドロキシ－４－プロピルオキシフェニル）－６－（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－オクチルオキシフェニル）－４，６－ビス（４－メチルフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－ドデシルオキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－［２－ヒドロキシ－４－（２－ヒドロキシ－３－ブチルオキシプロポキシ）フェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－［２－ヒドロキシ－４－（２－ヒドロキシ－３－オクチルオキシプロポキシ）フェニル］－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン等）、並びにシュウ酸アニリド類（例えば、Ｎ－（２－エチルフェニル）－Ｎ’－（２－エトキシ－５－ｔ－ブチルフェニル）シュウ酸ジアミド、Ｎ－（２－エチルフェニル）－Ｎ’－（２－エトキシ－フェニル）シュウ酸ジアミド、２－エトキシ－２’－エチル－オキサリック酸ビスアニリド、窒素原子上に置換されていてもよいアリール基等を有するシュウ酸ジアミド類等）等が挙げられる。 Examples of ultraviolet absorbers include salicylic acids (eg, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.), benzophenones (eg, 2,4-dihydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, etc.), benzotriazoles (for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5 ′) -Tert Butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-ditert -Amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole, etc.), triazines ( For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydride Xyl-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 -(2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2, 4-dimethyl Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, etc.), and oxalic anilides (eg, N- (2-ethylphenyl) -N ′-(2-ethoxy-5-tert-butylphenyl) oxalic acid diamide, N- (2-ethyl) Phenyl) -N ′-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2′-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group which may be substituted on the nitrogen atom, etc. ) And the like.
　ヒンダードアミン系光安定剤としては、例えば、エステル基含有ピペリジン類（例えば、４－アセトキシ－２，２，６，６－テトラメチルピペリジン、４－ステアロイルオキシ－２，２，６，６－テトラメチルピペリジン、４－アクリロイルオキシ－２，２，６，６－テトラメチルピペリジン等）、エーテル基含有ピペリジン類（例えば、４－メトキシ－２，２，６，６－テトラメチルピペリジン、４－シクロヘキシルオキシ－２，２，６，６－テトラメチルピペリジン、４－フェノキシ－２，２，６，６－テトラメチルピペリジン等）、アミド基含有ピペリジン類（例えば、４－（フェニルカルバモイルオキシ）－２，２，６，６－テトラメチルピペリジン、ビス（２，２，６，６－テトラメチル－４－ピペリジル）ヘキサメチレン－１，６－ジカルバメート等）、並びに、高分子量のピペリジン重縮合物類（例えば、コハク酸ジメチル－１－（２－ヒドロキシエチル）－４－ヒドロキシ－２，２，６，６－テトラメチルピペリジン重縮合物、１，２，３，４－ブタンテトラカルボン酸と１，２，２，６，６－ペンタメチル－４－ピペリジノールとトリデシルアルコールとの縮合物等）等が挙げられる。 Examples of the hindered amine light stabilizer include ester group-containing piperidines (for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine. 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, etc.), ether group-containing piperidines (for example, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2) , 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.), amide group-containing piperidines (for example, 4- (phenylcarbamoyloxy) -2,2,6 , 6-Tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1 6-dicarbamate, etc.), and high molecular weight piperidine polycondensates (eg, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate) And a condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol).
　本発明の分散液が光安定剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは１５重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下である。 When the dispersion of the present invention contains a light stabilizer, the amount thereof is preferably 0.01 parts by weight or more, preferably 15 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. The amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
＜紫外線硬化性オリゴマー＞
　紫外線硬化性オリゴマーとしては、例えば、ウレタンアクリレートオリゴマー、エポキシアクリレートオリゴマーおよびポリエステルアクリレートオリゴマー等が挙げられる。紫外線硬化性オリゴマーは、単独で使用してもよく、組み合わせて使用してもよい。 <Ultraviolet curable oligomer>
Examples of the ultraviolet curable oligomer include urethane acrylate oligomer, epoxy acrylate oligomer, and polyester acrylate oligomer. The ultraviolet curable oligomers may be used alone or in combination.
　ウレタンアクリレートオリゴマーは、市販のものを用いることができる。市販のウレタンアクリレートオリゴマーとしては、例えば、ＣＮ９２９、ＣＮ９６５、ＣＮ９６８、ＣＮ９８１Ａ７５、ＣＮ９８５Ｂ８８、ＣＮ９９１、ＣＮ９７０ＡＨ７５、ＣＮ９７５、ＣＮ９９２、ＣＮ９９４およびＣＮ９１６５（サートマー社製）、Ｕ－４ＨＡおよびＵ－６ＨＡ（新中村化学工業社製）、ＡＨ－６００、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＵＡ－５１０Ｈ、ＵＦ－８００１ＧおよびＤＡＵＡ－１６７（共栄社化学社製）等が挙げられる。 A commercially available urethane acrylate oligomer can be used. Examples of commercially available urethane acrylate oligomers include CN929, CN965, CN968, CN981A75, CN985B88, CN991, CN970AH75, CN975, CN992, CN994 and CN9165 (manufactured by Sartomer), U-4HA and U-6HA (Shin Nakamura Chemical Co., Ltd.) AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G and DAUA-167 (manufactured by Kyoeisha Chemical Co., Ltd.).
　エポキシアクリレートオリゴマーは、市販のものを用いることができる。市販のエポキシアクリレートオリゴマーとしては、例えば、ＣＮ１１６、ＣＮ１２０Ｂ６０、ＣＮ１２０Ｍ５０、ＣＮ１３１Ｂ、ＣＮ１３２、ＣＮ１３７、ＣＮ１５２および、ＣＮ２１０２Ｅ（サートマー社製）等が挙げられる。 A commercially available epoxy acrylate oligomer can be used. Examples of commercially available epoxy acrylate oligomers include CN116, CN120B60, CN120M50, CN131B, CN132, CN137, CN152, and CN2102E (manufactured by Sartomer).
　ポリエステルアクリレートオリゴマーは、市販のものを用いることができる。市販のポリエステルアクリレートオリゴマーとしては、例えば、ＣＮ２９２、ＣＮ２２５９、ＣＮ２２６２、ＣＮ２２７０、ＣＮ２２７１Ｅ、ＣＮ２２７２、ＣＮ２２７３、ＣＮ２２７６、ＣＮ２２７９、ＣＮ２２８５、ＣＮ２２９８、ＣＮ２３００、ＣＮ２３０１、ＣＮ２３０２、ＣＮ２３０３および、ＣＮ２３０４（サートマー社製）等が挙げられる。これらポリエステルアクリレートオリゴマーは、単独で使用してもよく、組み合わせて使用してもよい。 A commercially available polyester acrylate oligomer can be used. Examples of commercially available polyester acrylate oligomers include CN292, CN2259, CN2262, CN2270, CN2271E, CN2272, CN2273, CN2276, CN2279, CN2285, CN2298, CN2300, CN2301, CN2302, CN2303, and CN2304 (Cartomer). It is done. These polyester acrylate oligomers may be used alone or in combination.
　本発明の分散液が紫外線硬化性オリゴマーを含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは２０重量部以下、より好ましくは１５重量部以下、さらに好ましくは１０重量部以下、さらに一層好ましくは５重量部以下である。 When the dispersion of the present invention contains an ultraviolet curable oligomer, the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 20 parts by weight or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
＜蛍光増白剤＞
　蛍光増白剤としては、例えば、ジアルキルアミノクマリン、ビスジメチルアミノスチルベン、ビスメチルアミノスチルベン、４－アルコキシ－１，８－ナフタレンジカルボン酸－Ｎ－アルキルイミド、ビスベンズオキサゾリルエチレン、１，４－ビス（２－ベンゾオキサゾリル）ナフタレン、ジアルキルスチルベン等が挙げられる。市販の蛍光増白剤としては、例えば、Ｋａｙａｈｏｒ　３ＢＳ　Ｌｉｑ．、Ｋａｙａｈｏｒ　ＴＡＣ　Ｌｉｑ．、Ｋａｙａｐｈｏｒ　ＨＢＣ　Ｌｉｑ．、Ｋａｙａｌｉｇｈｔ　Ｂ、Ｋａｙａｐｈｏｒ　ＡＳ　１５０、Ｋａｙａｐｈｏｒ　ＣＲ　２００、Ｋａｙａｐｈｏｒ　ＪＢ　Ｌｉｑ．、Ｍｉｋａｗｈｉｔｅ　ＡＴＮ　ｃｏｎｃ．（日本化薬社製）、ＴＩＮＯＰＡＬ　ＯＢ、ＴＩＮＯＰＡＬ　ＮＦＷ　Ｌｉｑｉｄ（ＢＡＳＦ社製）、Ｈａｋｋｏｌ　Ｐ、Ｈａｋｋｏｌ　ＰＨＤ、Ｈａｋｋｏｌ　ＲＦ、Ｈａｋｋｏｌ　ＰＳＲ、Ｈａｋｋｏｌ　ＰＳＲ－Ｂ、Ｈａｋｋｏｌ　ＣＨＰ－Ｂ、Ｈａｋｋｏｌ　ＰＹ－２０００、Ｈａｋｋｏｌ　ＰＹＢ－Ｄ、Ｈａｋｋｏｌ　ＢＥ　ｃｏｎｃ、Ｈａｋｋｏｌ　ＳＧ　ｃｏｎｃ　１５０、Ｈａｋｋｏｌ　ＴＨ－１００、Ｈａｋｋｏｌ　Ｓ－１００、Ｈａｋｋｏｌ　ＲＸ－１、Ｈａｋｋｏｌ　ＯＷ－１１、Ｈａｋｋｏｌ　ＯＷ－１０ｅｘｔｒａ、Ｈａｋｋｏｌ　ＫＩＰ　Ｈ／Ｃ、Ｈａｋｋｏｌ　ＳＦ、Ｈａｋｋｏｌ　ＪＣ、および、Ｈａｋｋｏｌ　ＰＭＳ　Ｈ／Ｃ（昭和化学工業社製）、Ｎｉｋｋａｆｌｕｏｒ　ＳＢ　ｃｏｎｃ、Ｎｉｋｋａｆｌｕｏｒ　ＫＢ、Ｎｉｋｋａｆｌｕｏｒ　ＯＢ、Ｎｉｋｋａｂｒｉｇｈｔ　ＣＸ　Ｈ／Ｃ（日本化学工業所社製）等が挙げられる。蛍光増白剤は、単独で使用してもよく、２種以上を組み合わせて使用してもよい。 <Fluorescent brightener>
Examples of the optical brightener include dialkylaminocoumarin, bisdimethylaminostilbene, bismethylaminostilbene, 4-alkoxy-1,8-naphthalenedicarboxylic acid-N-alkylimide, bisbenzoxazolylethylene, 1,4 -Bis (2-benzoxazolyl) naphthalene, dialkylstilbene and the like. Examples of commercially available fluorescent whitening agents include Kayahor 3BS Liq. Kayahor TAC Liq. Kyaphor HBC Liq. Kayalight B, Kyaphor AS 150, Kyaphor CR 200, Kyaphor JB Liq. Mikawhite ATN conc. (Manufactured by Nippon Kayaku Co., Ltd.), TINOPAL OB, TINOPAL NFW Liqid (manufactured by BASF), Hakkol P, Hakkol PHD, Hakkol RF, Hakkol PSR, Hakkol PSR-B, Hakkol CYP-B, Hakkol PY-2000, Hakkol PY-2000 D, Hakkol BE conc, Hakkol SG conc 150, Hakkol TH-100, Hakkol S-100, Hakkol RX-1, Hakkol OW-11, Hakkol OW-10 extra, Hakkol KIP H / C, Hakol KIP H / C, Hakol Hakkol PMS H / C (manufactured by Showa Chemical Industry Co., Ltd.), Nikkafluor SB conc, Nikkafluor KB, Nikkafluor O B, Nikka bright CX H / C (manufactured by Nippon Chemical Industry Co., Ltd.) and the like. The optical brighteners may be used alone or in combination of two or more.
　本発明の分散液が蛍光増白剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは５重量部以下、より好ましくは３重量部以下、さらに好ましくは１重量部以下である。 When the dispersion of the present invention contains an optical brightener, the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 1 part by weight or less.
＜レベリング剤＞
　レベリング剤としては、例えば、ポリフローＮｏ．４５、ポリフローＫＬ－２４５、ポリフローＮｏ．７５、ポリフローＮｏ．９０、ポリフローＮｏ．９５（共栄社化学工業社製）、ＢＹＫ３００、ＢＹＫ３０６、ＢＹＫ３１０、ＢＹＫ３２０、ＢＹＫ３３０、ＢＹＫ３４６、ＢＹＫ３４９、ＢＹＫ－３３３、ＢＹＫ－３４５、ＢＹＫ－３４７、ＢＹＫ－３４８、ＢＹＫ－３７８（ビックケミー・ジャパン社製）、ＫＰ－３４１、ＫＰ－３５８、ＫＰ－３６８、ＫＦ－９６－５０ＣＳ、ＫＦ－５０－１００ＣＳ（信越化学工業社製）、サーフロンＳＣ－１０１、サーフロンＫＨ－４０（ＡＧＣセイミケミカル社製）、フタージェント２２２Ｆ、フタージェント２５１、ＦＴＸ－２１８（ネオス社製）、ＥＦＴＯＰ　ＥＦ－３５１、ＥＦＴＯＰ　ＥＦ－３５２、ＥＦＴＯＰ　ＥＦ－６０１、ＥＦＴＯＰ　ＥＦ－８０１、ＥＦＴＯＰ　ＥＦ－８０２（三菱マテリアル社製）、メガファックＦ－１７１、メガファックＦ－１７７、メガファックＦ－４７５、メガファックＦ－５５６、メガファックＲ－３０（ＤＩＣ社製）、アデカコールＷ－１９３、アデカコールＷ－２８７、アデカコールＷ－２８８、アデカコールＷ－３０４（ＡＤＥＫＡ社製）、ＳＮウェット３６６、ノプコ３８－Ｃ、ＳＮディスパーサンド５４６８、ＳＮディスパーサンド５０３４、ＳＮディスパーサンド５０２７、ＳＮディスパーサンド５０４０、ＳＮディスパーサンド５０２０（サンノプコ社）、フルオロアルキルベンゼンスルホン酸塩、フルオルアルキルカルボン酸塩、フルオロアルキルポリオキシエチレンエーテル、フルオロアルキルアンモニウムヨージド、フルオロアルキルベタイン、フルオロアルキルスルホン酸塩、ジグリセリンテトラキス（フルオロアルキルポリオキシエチレンエーテル）、フルオロアルキルトリメチルアンモニウム塩、フルオロアルキルアミノスルホン酸塩、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンラウレート、ポリオキシエチレンオレエート、ポリオキシエチレンステアレート、ポリオキシエチレンラウリルアミン、ソルビタンラウレート、ソルビタンパルミテート、ソルビタンステアレート、ソルビタンオレエート、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタンラウレート、ポリオキシエチレンソルビタンパルミテート、ポリオキシエチレンソルビタンステアレート、ポリオキシエチレンソルビタンオレエート、ポリオキシエチレンナフチルエーテル、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩等が挙げられる。 <Leveling agent>
As a leveling agent, for example, Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (manufactured by Kyoeisha Chemical Industries), BYK300, BYK306, BYK310, BYK320, BYK330, BYK346, BYK349, BYK-333, BYK-345, BYK-347, BYK-348, BYK-378 (manufactured by BYK Japan) KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (manufactured by Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40 (manufactured by AGC Seimi Chemical Co., Ltd.), Footgent 222F, footage 251, FTX-218 (manufactured by Neos), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (Mitsubishi Materials), MegaFuck F- 171 、 Me Fuck F-177, Mega Fuck F-475, Mega Fuck F-556, Mega Fuck R-30 (manufactured by DIC), Adeka Coal W-193, Adeka Coal W-287, Adeka Coal W-288, Adeka Coal W-304 (ADEKA) SN wet 366, Nopco 38-C, SN disperse sand 5468, SN disperse sand 5034, SN disperse sand 5027, SN disperse sand 5040, SN disper sand 5020 (San Nopco), fluoroalkylbenzene sulfonate, fluoroalkyl Carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl) Polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palm Tate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxy Chile Nso sorbitan monolaurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, alkyl diphenyl ether disulfonic acid salts.
　本発明の分散液がレベリング剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは１重量部以上であり、好ましくは２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下である。 When the dispersion of the present invention contains a leveling agent, the amount thereof is preferably 1 part by weight or more, preferably 20 parts by weight or less, based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group. More preferably, it is 10 parts by weight or less, and further preferably 5 parts by weight or less.
＜塩基性化合物＞
　塩基性化合物としては、例えば、アンモニア、有機アミン化合物および金属水酸化物等が挙げられる。塩基性化合物は、好ましくは、アンモニアまたは有機アミン化合物である。 <Basic compound>
As a basic compound, ammonia, an organic amine compound, a metal hydroxide, etc. are mentioned, for example. The basic compound is preferably ammonia or an organic amine compound.
　有機アミン化合物としては、例えば、トリエチルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、アミノエタノールアミン、Ｎ－メチル－Ｎ，Ｎ－ジエタノールアミン、イソプロピルアミン、イミノビスプロピルアミン、エチルアミン、ジエチルアミン、３－エトキシプロピルアミン、３－ジエチルアミノプロピルアミン、ｓｅｃ－ブチルアミン、プロピルアミン、メチルアミノプロピルアミン、３－メトキシプロピルアミン、モノエタノールアミン、モルホリン、Ｎ－メチルモルホリンおよびＮ－エチルモルホリン等が挙げられる。これらの中で、Ｎ，Ｎ－ジメチルエタノールアミンが好ましい。 Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine and N-ethylmorpholine. Of these, N, N-dimethylethanolamine is preferred.
　金属水酸化物としては、例えば、水酸化リチウム、水酸化カリウムおよび水酸化ナトリウム等が挙げられる。 Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide and sodium hydroxide.
　本発明の分散液が塩基性化合物を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下である。 When the dispersion of the present invention contains a basic compound, the amount thereof is preferably 0.01 parts by weight or more, preferably 20 parts per 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. The amount is not more than parts by weight, more preferably not more than 10 parts by weight, still more preferably not more than 5 parts by weight.
＜有機溶剤＞
　有機溶剤としては、例えば、トルエンおよびキシレン等の芳香族炭化水素類；ヘキサン等の脂肪族炭化水素類；酢酸エチルおよび酢酸ブチル等のエステル類；メチルエチルケトンおよびメチルイソブチルケトン等のケトン類；メタノ－ル、エタノール、ｎ－プロパノール、イソプロピルアルコールおよびｎ－ブタノール等のアルコール類；エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルおよび３－メトキシ－３－メチル－１－ブタノール等のグリコール類；メチルセロソルブ、セロソルブ、ブチルセロソルブ、ジオキサン、ＭＴＢＥ（メチルターシャリーブチルエーテル）およびブチルカルビトール等のセルソルブ類；エチレングリコールモノメチルエーテルアセテート、ＰＭＡ（プロピレングリコールモノメチルエーテルアセテート）、ジエチレングリコールモノブチルエーテルアセテートおよびジエチレングリコールモノエチルエーテルアセテート等のグリコールエステル類等が挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。 <Organic solvent>
Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; Alcohols such as ethanol, n-propanol, isopropyl alcohol and n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether and 3-methoxy-3 -Glycols such as methyl-1-butanol; methyl cellosolve, cellosolve, butyl cellosolve, dioxane, MTBE (methyl tertiary rib Ether) and butyl cellosolves of carbitol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol esters such as monobutyl ether acetate and diethylene glycol monoethyl ether acetate, and the like. These may be used alone or in combination of two or more.
　本発明の分散液中の有機溶剤の量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、臭気等の観点から、好ましくは０～１００重量部、より好ましくは０～５０重量部、さらに好ましくは０～３０重量部、さらに一層好ましくは０～１０重量部である。本発明の分散液が有機溶剤を含有しないことが特に好ましい。 The amount of the organic solvent in the dispersion of the present invention is preferably 0 to 100 parts by weight, more preferably 0, from the viewpoint of odor etc. with respect to the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. -50 parts by weight, more preferably 0-30 parts by weight, still more preferably 0-10 parts by weight. It is particularly preferred that the dispersion of the present invention does not contain an organic solvent.
＜架橋剤＞
　架橋剤を含むことにより、接着性、接着層の耐水性および接着層の耐溶剤性がより向上する傾向がある。架橋剤としては、例えば、エポキシ化合物、ポリイソシアネート化合物（特に、脂肪族ポリイソシアナネート化合物）、オキサゾリン化合物、アジリジン化合物、カルボジイミド化合物、活性メチロール化合物、活性アルコキシメチル化合物、金属キレート、ヒドラジド化合物、ヒドラジン化合物等が挙げられる。これらの中で、脂肪族ポリイソシアネート化合物、カルボジイミド化合物、オキサゾリン化合物、ヒドラジド化合物、ヒドラジン化合物が好ましい。中でも、水性（水溶性または水分散性）のものがさらに好ましい。これらの架橋剤は、単独で使用してもよく、組み合わせて使用してもよい。 <Crosslinking agent>
By including a crosslinking agent, there exists a tendency which adhesiveness, the water resistance of a contact bonding layer, and the solvent resistance of a contact bonding layer improve more. Examples of the crosslinking agent include epoxy compounds, polyisocyanate compounds (particularly aliphatic polyisocyanate compounds), oxazoline compounds, aziridine compounds, carbodiimide compounds, active methylol compounds, active alkoxymethyl compounds, metal chelates, hydrazide compounds, hydrazines. Compounds and the like. Among these, aliphatic polyisocyanate compounds, carbodiimide compounds, oxazoline compounds, hydrazide compounds, and hydrazine compounds are preferable. Among these, an aqueous one (water-soluble or water-dispersible) is more preferable. These crosslinking agents may be used alone or in combination.
　ポリイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート（ＨＤＩ）、４，４’－ジフェニルメタンジイソシアネート（ＭＤＩ）、トリレンジイソシアネート（ＴＤＩ）および、これらのオリゴマーまたはポリマー等が挙げられる。その具体例としては、住化コベストロウレタン製のスミジュール（登録商標）Ｎ３２００、Ｎ３３００、Ｎ３４００、Ｎ３６００、Ｎ３９００、Ｓ－３０４、Ｓ－３０５、ＸＰ－２６５５、ＸＰ－２４８７、ＸＰ－２５４７、４４Ｖ１０、４４Ｖ２０およびＥ　２１－１、住友コベストロウレタン社製のデスモジュール（登録商標）Ｎ３１００、Ｎ３３００、Ｎ３４００、Ｎ３６００、Ｎ３９００、Ｓ－３０４、Ｓ－３０５、ＸＰ－２６５５、ＸＰ－２４８７、ＸＰ－２５４７およびＤＡ－Ｌ、Ｅ１４およびＥ　２２、住友コベストロウレタン社製のバイヒジュール（登録商標）３０４およびＸＰ２６５５、ＢＡＳＦ社製のバソナート（ＢＡＳＯＮＡＴ（登録商標））ＰＬＲ８８７８およびＨＷ－１００、武田薬品工業社製のタケネート（登録商標）ＷＤ７２０、ＷＤ７２５およびＷＤ７３０、旭化成工業社製のデュラネート（登録商標）ＷＢ４０－１００、ＷＢ４０－８０ＤおよびＷＸ－１７４１等が挙げられる。 Examples of the polyisocyanate compound include hexamethylene diisocyanate (HDI), 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and oligomers or polymers thereof. Specific examples thereof include Sumidur (registered trademark) N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, 44V10 made by Sumika Covestrourethane. , 44V20 and E 21-1, Death Module (registered trademark) N3100, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547, manufactured by Sumitomo Covestrourethane Co., Ltd. DA-L, E14 and E 22, Bihijoule (registered trademark) 304 and XP2655 manufactured by Sumitomo Covestrourethane, Basonat (BASONAT (registered trademark)) PLR8878 and HW-100 manufactured by BASF, manufactured by Takeda Pharmaceutical Company Limited Takenate Trademark) WD720, WD725, and WD730, Asahi Chemical Industry Co. Duranate (registered trademark) WB40-100, include WB40-80D and WX-1741 or the like.
　カルボジイミド化合物の具体例としては、日清紡ケミカル（株）：カルボジライト（ＳＶ－０２、Ｖ－０２、Ｖ－０２－Ｌ、Ｖ－０４、Ｅ－０１、Ｅ－０２）等が挙げられる。 Specific examples of the carbodiimide compound include Nisshinbo Chemical Co., Ltd .: Carbodilite (SV-02, V-02, V-02-L, V-04, E-01, E-02) and the like.
　ヒドラジド化合物の具体例としては、大塚化学（株）：ＡＤＨ（アジピン酸ジヒドラジド）、ＳＤＨ（セバシン酸ジヒドラジド）、ＤＤＨ（ドデカンジオヒドラジド）、ＩＤＨ（イソフタル酸ジヒドラジド）、ＳＡＨ（サリチル酸ヒドラジド）等が挙げられる。 Specific examples of hydrazide compounds include Otsuka Chemical Co., Ltd .: ADH (adipic acid dihydrazide), SDH (sebacic acid dihydrazide), DDH (dodecandiohydrazide), IDH (isophthalic acid dihydrazide), SAH (salicylic acid hydrazide) and the like. It is done.
　ヒドラジン化合物の具体例としては、大塚化学（株）：モノ塩酸ヒドラジン、ジ塩酸ヒドラジン、モノ臭化水素酸ヒドラジン、炭酸ヒドラジン等が挙げられる。 Specific examples of the hydrazine compound include Otsuka Chemical Co., Ltd .: hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.
　本発明の分散液が架橋剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは３０重量部以下、より好ましくは１５重量部以下、さらに好ましくは１０重量部以下、さらに一層好ましくは５重量部以下である。 When the dispersion of the present invention contains a crosslinking agent, the amount thereof is preferably 0.01 parts by weight or more, preferably 30 parts by weight with respect to a total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Part or less, more preferably 15 parts by weight or less, further preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
＜光増感剤＞
　光増感剤は、増強したい波長に応じて適宜選定することができる。光増感剤の有効励起波長域は、通常、４５０ｎｍ以下であり、好ましくは２５０～３８０ｎｍである。光増感剤としては、例えば、トリエタノールアミン、トリイソプロパノールアミン、４，４－ジエチルアミノベンゾフェノン、２－ジメチルアミノエチル安息香酸、４－ジメチルアミノエチル安息香酸エチルおよび４－ジメチルアミノ安息香酸イソアシル等が挙げられる。 <Photosensitizer>
The photosensitizer can be appropriately selected according to the wavelength to be enhanced. The effective excitation wavelength range of the photosensitizer is usually 450 nm or less, preferably 250 to 380 nm. Examples of photosensitizers include triethanolamine, triisopropanolamine, 4,4-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminoethylbenzoate, and isoacyl 4-dimethylaminobenzoate. Can be mentioned.
　本発明の分散液が光増感剤を含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは１５重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下である。 When the dispersion of the present invention contains a photosensitizer, the amount is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, preferably 100 parts by weight in total of the chlorinated rubber and the compound having a polymerizable group. It is 15 parts by weight or less, more preferably 10 parts by weight or less, and still more preferably 5 parts by weight or less.
＜他の樹脂またはゴム＞
　本発明の分散液は、本発明の効果を損なわない範囲で、塩素化ゴムとは異なる他の樹脂またはゴムを含有してもよい。他の樹脂またはゴムは、いずれも、１種のみを使用してもよく、２種以上を併用してもよい。なお、本明細書においてゴムとは、弾性を有するエラストマーを意味し、樹脂とは、弾性を有さない熱可塑性樹脂または熱硬化性樹脂を意味する。 <Other resin or rubber>
The dispersion of the present invention may contain another resin or rubber different from the chlorinated rubber as long as the effects of the present invention are not impaired. Any other resin or rubber may be used alone or in combination of two or more. In this specification, rubber means an elastomer having elasticity, and resin means a thermoplastic resin or thermosetting resin that does not have elasticity.
　他の樹脂またはゴムとしては、例えば、エチレン－ビニルエステル共重合体、スチレン－マレイン酸共重合体、炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂および変性物、（メタ）アクリル系樹脂、ポリスチレン、ポリ酢酸ビニル、ポリウレタン、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩化ビニル－酢酸ビニル共重合体、塩化ビニル－アクリル酸エステル共重合体、塩化ビニル－塩化ビニリデン共重合体、塩化ビニリデン－（メタ）アクリル酸エステル共重合体、塩化ビニリデン－アクリロニトリル共重合体、塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂、ポリウレア、アクリロニトリル－ブタジエン－スチレン共重合体、クロロプレン系樹脂、酸変性クロロプレン系樹脂、ブチルゴム、臭素化ブチルゴム、変性ゴム、スチレン－（メタ）アクリル酸共重合体、合成ゴム、天然ゴム、スチレン－ブタジエン共重合体、ポリブタジエン、ポリ（メタ）アクリロニトリル、ポリ（メタ）アクリルアミド、ポリエステル、変性ポリアミド、エポキシ樹脂、スチレン系ブロック共重合体およびこれらのオリゴマー等が挙げられる。他の樹脂またはゴムは、固体（例えば、樹脂またはゴムの粉末）の形態であってもよいし、エマルションの形態であってもよい。 Examples of other resins or rubbers include ethylene-vinyl ester copolymers, styrene-maleic acid copolymers, resins having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and modified products, (meth) acrylic Resin, polystyrene, polyvinyl acetate, polyurethane, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-vinylidene chloride Polymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride-acrylonitrile copolymer, chlorinated resin having a structural unit derived from α-olefin having 2 to 20 carbon atoms, polyurea, acrylonitrile-butadiene -Styrene copolymer, chloroprene resin, acid-modified chloroprene Resin, butyl rubber, brominated butyl rubber, modified rubber, styrene- (meth) acrylic acid copolymer, synthetic rubber, natural rubber, styrene-butadiene copolymer, polybutadiene, poly (meth) acrylonitrile, poly (meth) acrylamide, Examples include polyesters, modified polyamides, epoxy resins, styrenic block copolymers, and oligomers thereof. The other resin or rubber may be in the form of a solid (for example, resin or rubber powder) or in the form of an emulsion.
　エチレン－ビニルエステル共重合体とは、エチレン単位およびビニルエステル単位を含む共重合体である。ビニルエステル単位としては、例えば、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、炭素数８～１０の３級カルボン酸のビニルエステルおよびいわゆるバーサチック酸ビニル（例えば、シェル化学社製、商品名：Ｖｅｏｖａ（登録商標）１０）等のアルキル酸ビニルエステルに由来する単位等が挙げられる。 The ethylene-vinyl ester copolymer is a copolymer containing an ethylene unit and a vinyl ester unit. Examples of the vinyl ester unit include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester of tertiary carboxylic acid having 8 to 10 carbon atoms and so-called vinyl versatate (for example, trade name: Veova (manufactured by Shell Chemical Co., Ltd.). Units derived from alkyl acid vinyl esters such as (registered trademark) 10).
　エチレン－ビニルエステル共重合体は、エチレン単位、ビニルエステル単位の他に、エチレンおよびビニルエステルと共重合可能な単量体に由来する単位を含有してもよい。この単量体としては、例えば、塩化ビニル等のハロゲン化ビニル、少量のアミド基等の官能基をもつ単量体、（メタ）アクリル酸エステル等が挙げられる。 The ethylene-vinyl ester copolymer may contain units derived from monomers copolymerizable with ethylene and vinyl esters, in addition to ethylene units and vinyl ester units. Examples of this monomer include vinyl halides such as vinyl chloride, monomers having a small amount of functional groups such as amide groups, and (meth) acrylic acid esters.
　エチレン－ビニルエステル共重合体の中でも、エチレン－酢酸ビニル共重合体（以下、「ＥＶＡ」と略することがある。）が好ましい。 Among the ethylene-vinyl ester copolymers, an ethylene-vinyl acetate copolymer (hereinafter sometimes abbreviated as “EVA”) is preferable.
　エチレン－酢酸ビニル共重合体は、酢酸ビニルの含有率等によって性質が異なるが、種々の酢酸ビニル含有率および形状（フィルム、ブロック、繊維、発泡体）のものを使用することができる。エチレン－酢酸ビニル共重合体は、エチレン単位以外の他のオレフィン単位を含有していてもよい。他のオレフィン単位を含有するエチレン－酢酸ビニル共重合体としては、例えば、エチレン－オクテン－酢酸ビニル共重合体、エチレン－ブテン－酢酸ビニル共重合体、エチレン－プロピレン－酢酸ビニル共重合体が挙げられる。 The ethylene-vinyl acetate copolymer has different properties depending on the vinyl acetate content and the like, but various vinyl acetate contents and shapes (films, blocks, fibers, foams) can be used. The ethylene-vinyl acetate copolymer may contain olefin units other than ethylene units. Examples of the ethylene-vinyl acetate copolymer containing other olefin units include ethylene-octene-vinyl acetate copolymer, ethylene-butene-vinyl acetate copolymer, and ethylene-propylene-vinyl acetate copolymer. It is done.
　エチレン－ビニルエステル共重合体としては、例えば、ＶＩＮＮＯL Ｅ１５／４５、Ｅ１５／４５Ｍ、Ｅ１５／４８Ａ、Ｈ１５／４２、Ｈ１５／５０、Ｈ１１／５９、Ｈ１４／３６、Ｈ４０／５０、Ｈ４０／５５、Ｈ４０／６０、Ｈ３０／４８Ｍ（Ｗａｃｋｅｒ　Ｃｈｅｍｉｅ　ＡＧ社）等が挙げられる。 Examples of the ethylene-vinyl ester copolymer include VINNOL® E15 / 45, E15 / 45M, E15 / 48A, H15 / 42, H15 / 50, H11 / 59, H14 / 36, H40 / 50, H40 / 55, and H40. / 60, H30 / 48M (Wacker Chemie AG) and the like.
　エチレン－ビニルエステル共重合体は、エマルションの形態であってもよい。このようなエマルションは、前記エチレン単位およびビニルエステル単位を構成する単量体を乳化重合することによって製造してもよいし、市販のものを用いてもよい。エチレン－ビニルエステル共重合体のエマルションとしては、例えば、スミカフレックス（登録商標）２０１ＨＱ、３０３ＨＱ、３５５ＨＱ、４００ＨＱ、４０１ＨＱ、４０８ＨＱ、４１０ＨＱ、４５０ＨＱ、４５５ＨＱ、４５６ＨＱ、４６０ＨＱ、４６５ＨＱ、４６７ＨＱ、７４００ＨＱ、４７０ＨＱ、４７８ＨＱ、５１０ＨＱ、５２０ＨＱ、７１０、７５２、７５５、ＳＤＸ－５１００、８０１ＨＱ、８０８ＨＱ、８３０、８５０ＨＱ、９００ＨＬおよび３９５０（以上、住友化学（株）製）、バンフレックスＯＭ－４０００およびＯＭ－４２００（以上、（株）クラレ製）、ポリゾール（登録商標）ＥＶＡ　ＡＤ－２、ＡＤ－３、ＡＤ－４、ＡＤ－５、ＡＤ－５１、ＡＤ－５６、ＡＤ－５９およびＰ－９００（以上、昭和高分子（株）製）、デンカＥＶＡテックス（登録商標）＃２０、＃３０、＃４０Ｍ、＃６０、＃８１および＃８２（以上、デンカ（株）製）等が挙げられる。 The ethylene-vinyl ester copolymer may be in the form of an emulsion. Such an emulsion may be produced by emulsion polymerization of monomers constituting the ethylene unit and the vinyl ester unit, or a commercially available product may be used. Examples of the emulsion of the ethylene-vinyl ester copolymer include Sumikaflex (registered trademark) 201HQ, 303HQ, 355HQ, 400HQ, 401HQ, 408HQ, 410HQ, 450HQ, 455HQ, 456HQ, 460HQ, 465HQ, 467HQ, 7400HQ, 470HQ, 478HQ, 510HQ, 520HQ, 710, 752, 755, SDX-5100, 801HQ, 808HQ, 830, 850HQ, 900HL and 3950 (above, manufactured by Sumitomo Chemical Co., Ltd.), Vanflex OM-4000 and OM-4200 (above, (Manufactured by Kuraray Co., Ltd.), Polysol (registered trademark) EVA AD-2, AD-3, AD-4, AD-5, AD-51, AD-56, AD-59 and P-900 (above, Showa Polymer) (stock) ), Denka EVA TEX (registered trademark) # 20, # 30, # 40M, # 60, # 81 and # 82 (above, Denka Co., Ltd.).
　スチレン－マレイン酸共重合体としては、例えば、アラスター７００、７０３Ｓ（荒川化学工業（株）製）、ＳＭＡ（登録商標）１０００、ＳＭＡ（登録商標）２０００、ＳＭＡ（登録商標）３０００（Ｃｒａｙ　Ｖａｌｌｅｙ’ｓ　社製）等が挙げられる。スチレン－マレイン酸共重合体のエマルションとしては、例えば、ＶＥ－１１２２（星光ＰＭＣ（株）製）等が挙げられる。 Examples of the styrene-maleic acid copolymer include ARASTOR 700, 703S (manufactured by Arakawa Chemical Industry Co., Ltd.), SMA (registered trademark) 1000, SMA (registered trademark) 2000, SMA (registered trademark) 3000 (Cray Valley '). s). Examples of the styrene-maleic acid copolymer emulsion include VE-1122 (manufactured by Seiko PMC Co., Ltd.).
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂は、単独重合体、ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれでもよい。また、過酸化物等で低分子量化、高分子量化したものであってもよい。 The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms may be any of a homopolymer, a random copolymer, a block copolymer, and a graft copolymer. Further, it may be reduced in molecular weight or high molecular weight by peroxide or the like.
　炭素数２～２０のα－オレフィンとしては、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－へプテン、１－オクテン、１－ノネン、１－デセン、１－ウンデセン、１－ドデセン、１－トリデセン、１－テトラデセン、１－ペンタデセン、１－ヘキサデセン、１－ヘプタデセン、１－オクタデセン、１－ノナデセン、１－エイコセンおよびビニルシクロヘキサン等が挙げられる。これらの中で、エチレン、プロピレンが好ましい。 Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and vinylcyclohexane. Of these, ethylene and propylene are preferred.
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂としては、例えば、ポリエチレン（ＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン、超高分子量ポリエチレンおよびポリプロピレン（ＰＰ）、アイソタクチック（イソタクチック）ポリプロピレン、シンジオタクチックポリプロピレンおよびアタクチックポリプロピレン等のα－オレフィン系単独重合体；エチレン－プロピレン共重合体、プロピレン－１－ブテン共重合体、エチレン－１－ブテン共重合体、エチレン－１－オクテン共重合体およびエチレン－１－ヘキセン共重合体等のα－オレフィン系共重合体；および炭素数２～２０のα－オレフィンと該α－オレフィンと共重合可能な単量体との共重合体が挙げられる。また、炭素数２～２０のα－オレフィンと該α－オレフィンと共重合可能な単量体との共重合体は、それぞれに由来する単位を１種類ずつ含むものであってもよいし、それぞれに由来する単位を２種類以上含むものであってもよい。 Examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include polyethylene (PE), high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear Α-olefin homopolymers such as low density polyethylene, ultra high molecular weight polyethylene and polypropylene (PP), isotactic (isotactic) polypropylene, syndiotactic polypropylene and atactic polypropylene; ethylene-propylene copolymer, propylene-1 An α-olefin copolymer such as a butene copolymer, an ethylene-1-butene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-hexene copolymer; and an α having 2 to 20 carbon atoms -Copolymerizable with olefin and α-olefin And a copolymer with a functional monomer. Further, the copolymer of an α-olefin having 2 to 20 carbon atoms and a monomer copolymerizable with the α-olefin may contain one type of unit derived from each, It may contain two or more types of units derived from.
　炭素数２～２０のα－オレフィンと共重合可能な単量体としては、例えば、α，β－不飽和カルボン酸およびその無水物、α，β－不飽和カルボン酸の金属塩、α，β－不飽和カルボン酸エステル、ビニルエステル、ビニルエステル鹸化物、環状オレフィン、ビニル芳香族化合物、ポリエン化合物（ジエン類等）、（メタ）アクリロニトリル、ハロゲン化ビニル類、アミドおよびハロゲン化ビリニデン類等が挙げられる。これらは単独で用いてもよく、組み合わせて用いてもよい。 Examples of monomers copolymerizable with an α-olefin having 2 to 20 carbon atoms include, for example, α, β-unsaturated carboxylic acids and their anhydrides, metal salts of α, β-unsaturated carboxylic acids, α, β -Unsaturated carboxylic acid esters, vinyl esters, vinyl ester saponified products, cyclic olefins, vinyl aromatic compounds, polyene compounds (dienes, etc.), (meth) acrylonitrile, vinyl halides, amides and halogenated vinylidenes, etc. It is done. These may be used alone or in combination.
　α，β－不飽和カルボン酸およびその無水物としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸のハーフエステル、マレイン酸のハーフアミド、イタコン酸のハーフエステルおよびイタコン酸のハーフアミド等が挙げられる。なかでもアクリル酸、メタクリル酸、マレイン酸および無水マレイン酸が好ましく、特にアクリル酸および無水マレイン酸が好ましい。 Examples of the α, β-unsaturated carboxylic acid and its anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, monomethyl maleate, monoethyl maleate , Maleic acid half ester, maleic acid half amide, itaconic acid half ester, itaconic acid half amide, and the like. Of these, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
　α，β－不飽和カルボン酸の金属塩としては、例えば、リチウム、ナトリウム、カリウム等の１価金属の塩、マグネシウム、カルシウム、亜鉛等の多価金属の塩が挙げられる。具体的には、（メタ）アクリル酸のナトリウム塩およびマグネシウム塩が挙げられる。 Examples of the metal salt of α, β-unsaturated carboxylic acid include salts of monovalent metals such as lithium, sodium and potassium, and salts of polyvalent metals such as magnesium, calcium and zinc. Specifically, the sodium salt and magnesium salt of (meth) acrylic acid are mentioned.
　α，β－不飽和カルボン酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、２－ヒドロキシエチルアクリレート、マレイン酸ジメチルおよびメタクリル酸とアルコールとのエステル化物等が挙げられる。なかでも、メチル（メタ）アクリレートおよびエチル（メタ）アクリレートが好ましい。 Examples of the α, β-unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, Examples thereof include dimethyl maleate and esterified products of methacrylic acid and alcohol. Of these, methyl (meth) acrylate and ethyl (meth) acrylate are preferred.
　ビニルエステルとしては、例えば、ぎ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニルおよびバーサチック酸ビニル等が挙げられる。なかでも、酢酸ビニルが好ましい。 Examples of vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl versatate. Of these, vinyl acetate is preferred.
　ビニルエステル鹸化物としては、例えば、ビニルエステルを塩基性化合物等でケン化して得られるビニルアルコール等が挙げられる。 Examples of the vinyl ester saponified product include vinyl alcohol obtained by saponifying vinyl ester with a basic compound or the like.
　環状オレフィンとしては、例えば、ノルボルネン、５－メチルノルボルネン、５－エチルノルボルネン、１，４，５，８－ジメタノ－１，２，３，４，４ａ，５，８，８ａ－オクタヒドロナフタレン、１，２－ジヒドロジシクロペンタジエン、５－クロロノルボルネン、シクロペンテン、シクロへキセン、シクロへプテンおよびビニルシクロヘキサン等が挙げられる。 Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1 , 2-dihydrodicyclopentadiene, 5-chloronorbornene, cyclopentene, cyclohexene, cycloheptene, vinylcyclohexane and the like.
　ビニル芳香族化合物としては、例えば、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ビニルキシレン、モノクロロスチレン、ジクロロスチレン、モノブロモスチレン、ジブロモスチレン、フルオロスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、エチルスチレンおよびビニルナフタレン等が挙げられる。 Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and Examples include vinyl naphthalene.
　ポリエン化合物としては、例えば、直鎖状または分岐状の脂肪族共役ポリエン化合物、脂環式共役ポリエン化合物、脂肪族非共役ポリエン化合物、脂環式非共役ポリエン化合物および芳香族非共役ポリエン化合物等が挙げられる。これらは、アルコキシ基、アリール基、アリールオキシ基、アラルキル基およびアラルキルオキシ基等の置換基を有していてもよい。 Examples of polyene compounds include linear or branched aliphatic conjugated polyene compounds, alicyclic conjugated polyene compounds, aliphatic non-conjugated polyene compounds, alicyclic non-conjugated polyene compounds, and aromatic non-conjugated polyene compounds. Can be mentioned. These may have a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.
　脂肪族共役ポリエン化合物としては、例えば、１，３－ブタジエン、イソプレン、２－エチル－１，３－ブタジエン、２－プロピル－１，３－ブタジエン、２－イソプロピル－１，３－ブタジエン、２－メチル－１，３－デカジエン、２，３－ジメチル－１，３－ペンタジエン、２，３－ジメチル－１，３－オクタジエンおよび２，３－ジメチル－１，３－デカジエン等が挙げられる。 Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2- Examples include methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, and 2,3-dimethyl-1,3-decadiene.
　脂環式共役ポリエン化合物としては、例えば、２－メチル－１，３－シクロペンタジエン、２－メチル－１，３－シクロヘキサジエン、２，３－ジメチル－１，３－シクロヘキサジエン、２－クロロ－１，３－ブタジエン、２－クロロ－１，３－ペンタジエンおよび２－クロロ－１，３－シクロヘキサジエン等が挙げられる。 Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro- Examples include 1,3-butadiene, 2-chloro-1,3-pentadiene and 2-chloro-1,3-cyclohexadiene.
　脂肪族非共役ポリエン化合物としては、例えば、１，４－ヘキサジエン、１，６－ヘプタジエン、１，６－オクタジエン、１，９－デカジエン、３，３－ジメチル－１，４－ヘキサジエン、５－エチル－１，４－ヘプタジエン、４－メチル－１，４－オクタジエン、５－メチル－１，４－オクタジエン、４－エチル－１，４－オクタジエン、４－メチル－１，４－ノナジエン、５－メチル－１，４－デカジエン、６－メチル－１，６－ウンデカジエンおよび４－エチリデン－１２－メチル－１，１１－ペンタデカジエン等が挙げられる。 Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,9-decadiene, 3,3-dimethyl-1,4-hexadiene, and 5-ethyl. -1,4-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 4-methyl-1,4-nonadiene, 5-methyl -1,4-decadiene, 6-methyl-1,6-undecadiene, 4-ethylidene-12-methyl-1,11-pentadecadien, and the like.
　脂環式非共役ポリエン化合物としては、例えば、ビニルシクロヘキサン、ビニルシクロヘキセン、５－ビニル－２－ノルボルネン、１，４－ジビニルシクロヘキサン、１－イソプロペニル－３－ビニルシクロペンタンおよびメチルテトラヒドロインデン等が挙げられる。 Examples of the alicyclic non-conjugated polyene compound include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 1,4-divinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane, and methyltetrahydroindene. It is done.
　芳香族非共役ポリエン化合物としては、例えば、ジビニルベンゼンおよびビニルイソプロペニルベンゼン等が挙げられる。 Examples of the aromatic non-conjugated polyene compound include divinylbenzene and vinylisopropenylbenzene.
　炭素数２～２０のα－オレフィン由来の構造単位を有する共重合体としては、例えば、エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体のようなエチレン不飽和カルボン酸共重合体、前記エチレン－不飽和カルボン酸共重合体のカルボキシル基の一部または全部が金属で中和されたアイオノマー、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－メタクリル酸メチル共重合体、エチレン－アクリル酸イソブチル共重合体、エチレン－アクリル酸ｎブチル共重合体のようなエチレン－不飽和カルボン酸エステル共重合体、エチレン－アクリル酸イソブチル－メタクリル酸共重合体、エチレン－アクリル酸ｎブチル－メタクリル酸共重合体のようなエチレン－不飽和カルボン酸エステル－不飽和カルボン酸共重合体およびそのカルボキシル基の一部または全部が金属で中和されたアイオノマー等が挙げられる。 Examples of the copolymer having a structural unit derived from an α-olefin having 2 to 20 carbon atoms include an ethylene unsaturated carboxylic acid copolymer such as an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer, Ionomers in which some or all of the carboxyl groups of the ethylene-unsaturated carboxylic acid copolymer are neutralized with metal, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate Copolymer, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-isobutyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate-methacrylic acid copolymer, ethylene- Ethylene-unsaturated carboxylic acid ester such as n-butyl acrylate-methacrylic acid copolymer - and ionomer in which part or all of the unsaturated carboxylic acid copolymer and its carboxyl groups neutralized with metal.
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の変性物としては、例えば、炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂をα，β－不飽和カルボン酸類等により変性して得られる変性物が挙げられる。 Examples of modified products having structural units derived from α-olefins having 2 to 20 carbon atoms include resins having structural units derived from α-olefins having 2 to 20 carbon atoms such as α, β-unsaturated carboxylic acids, etc. The modified product obtained by modification | denaturation by is mentioned.
　α，β－不飽和カルボン酸類等による変性率は、変性前の炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂１００重量％に対して、好ましくは０．１～１０重量％、より好ましくは０．２～５重量％、さらに好ましくは０．２～４重量％である。 The modification rate with α, β-unsaturated carboxylic acids and the like is preferably 0.1 to 10% by weight with respect to 100% by weight of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms before modification, More preferably, it is 0.2 to 5% by weight, and still more preferably 0.2 to 4% by weight.
　α，β－不飽和カルボン酸類としては、例えば、α，β－不飽和カルボン酸（マレイン酸、イタコン酸、シトラコン酸等）、α，β－不飽和カルボン酸エステル（マレイン酸メチル、イタコン酸メチル、シトラコン酸メチル等）、α，β－不飽和カルボン酸無水物（無水マレイン酸、無水イタコン酸、無水シトラコン酸等）が挙げられる。炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の変性には、α，β－不飽和カルボン酸類の１種のみを使用してもよく、その２種以上を併用してもよい。 Examples of α, β-unsaturated carboxylic acids include α, β-unsaturated carboxylic acids (maleic acid, itaconic acid, citraconic acid, etc.), α, β-unsaturated carboxylic acid esters (methyl maleate, methyl itaconate) ), Α, β-unsaturated carboxylic anhydrides (maleic anhydride, itaconic anhydride, citraconic anhydride, etc.). For modification of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, only one of α, β-unsaturated carboxylic acids may be used, or two or more of them may be used in combination. .
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の変性物は、前記樹脂を溶融させた後、溶融物にα，β－不飽和カルボン酸類等を添加して、前記樹脂を変性させる方法、トルエン、キシレン等の有機溶剤に前記樹脂を溶解した後、その溶液にα，β－不飽和カルボン酸類等を添加して、前記樹脂を変性させる方法等によって製造することができる。 A modified product of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is obtained by melting the resin and then adding an α, β-unsaturated carboxylic acid or the like to the melt. The resin can be prepared by, for example, a method of dissolving the resin in an organic solvent such as toluene or xylene and then adding an α, β-unsaturated carboxylic acid or the like to the solution to modify the resin.
　塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の塩素化率としては、変性前の共重合体１００重量％に対して、好ましくは５～８０重量％であり、より好ましくは４０～７５重量％であり、さらに好ましくは５５～７０重量％である。 The chlorination rate of the chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is preferably 5 to 80% by weight with respect to 100% by weight of the copolymer before modification, More preferably, it is 40 to 75% by weight, and further preferably 55 to 70% by weight.
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の塩素化は、炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂を有機溶剤に溶解または分散し、得られた混合物に塩素ガスを吹き込む方法等によって行うことができる。 Chlorination of a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms is obtained by dissolving or dispersing the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms in an organic solvent. It can be performed by a method of blowing chlorine gas into the chamber.
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂およびその変性物としては、例えば、メルセン（登録商標）Ｈ－６４１０Ｍ、Ｈ－６０５１、Ｈ－６９６０、Ｈ－６８２０およびＨ－６８２２Ｘ（東ソー（株））、エバール（登録商標）Ｌ１７１Ｂ、Ｆ１７１Ｂ、Ｈ１７１Ｂ、Ｅ１０５ＢおよびＧ１５６Ｂ（（株）クラレ）、ソアノール（登録商標）Ｄ２９０８、ＤＴ２９０４、ＤＣ３２１２、ＤＣ３２０３、Ｅ３８０８、ＥＴ３８０３、Ａ４４１２、ＡＴ４４０３、ＢＸ、１６ＤＸ、Ｄ２９０８Ｈ４およびＡ４４１２Ｈ４（日本合成化学工業（株））、ソアレジン（登録商標）ＰＧ５０５（日本合成化学工業（株））、ＮＩＳＳＯ（登録商標）ＰＢ（日本曹達（株））、ポリテール（登録商標）Ｈ（三菱化学（株））、エポール（登録商標）（出光興産（株））、ＯＲＥＶＡＣ（登録商標）Ｇ　１８２１１、ＯＥ８０８およびＯＥ８２５（アルケマ（株））、ＬＯＴＡＤＡＲ　ＭＡＨ２２１０、３２００、Ｐ３　３２００、３２１０、４２１０、６２００、３４１０、３４３０および４７２０（アルケマ（株））、ＢＯＮＤＩＮＥ（登録商標）ＬＸ４１１０、ＨＸ８２１０、ＴＸ８０３０、ＨＸ８２９０、ＨＸ８４１０およびＡＸ８３９０（アルケマ（株））、ＯＲＥＶＡＣ（登録商標）Ｔ９３１４、Ｔ９３１８およびＧ１８２１１（アルケマ（株））、ユーメックス（登録商標）２０００（三洋化成工業（株））、並びにアウローレン（登録商標）１００Ｓおよび２００Ｔ（日本製紙ケミカル（株））等が挙げられる。 Examples of the resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and modified products thereof include, for example, Mersen (registered trademark) H-6410M, H-6051, H-6960, H-6820, and H-6822X ( Tosoh Corporation), EVAL (registered trademark) L171B, F171B, H171B, E105B and G156B (Kuraray Co., Ltd.), Soarnol (registered trademark) D2908, DT2904, DC3212, DC3203, E3808, ET3803, A4412, AT4403, BX, 16DX, D2908H4 and A4412H4 (Nippon Synthetic Chemical Industry Co., Ltd.), Soaredin (registered trademark) PG505 (Nippon Synthetic Chemical Industry Co., Ltd.), NISSO (registered trademark) PB (Nippon Soda Co., Ltd.), Polytail (registered trademark) H (Mitsubishi Chemical Corporation), Epo LE (registered trademark) (Idemitsu Kosan Co., Ltd.), OREVAC (registered trademark) G 18211, OE808 and OE825 (Arkema Co., Ltd.), LOTADAR MAH2210, 3200, P3 3200, 3210, 4210, 6200, 3410, 3430 and 4720 (Arkema Corp.), BONDINE (registered trademark) LX4110, HX8210, TX8030, HX8290, HX8410 and AX8390 (Arkema Corp.), OREVAC (registered trademark) T9314, T9318 and G18211 (Arkema Corp.), Umex (registered) (Trademark) 2000 (Sanyo Chemical Industry Co., Ltd.) and Auroren (registered trademark) 100S and 200T (Nippon Paper Chemicals Co., Ltd.).
　炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂およびその変性物は、エマルションの形態であってもよい。このようなエマルションは、炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂およびその変性物を乳化することによって製造してもよいし、市販のものを用いてもよい。炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂およびその変性物のエマルションとしては、例えば、アローベース（登録商標）ＳＡ－１２００、ＳＢ－１２００、ＳＥ－１２００、ＳＢ－１０１０（ユニチカ（株））、アプトロック（登録商標）ＢＷ－５５５０（三菱化学（株））、アウローレン（登録商標）ＡＥ－２０２、ＡＥ－３０１（日本製紙（株））、アクアテックス（登録商標）ＥＣ－１２００、ＥＣ－１７００、ＡＣ－３１００、ＭＣ－４４００、ＨＡ－１１００、９０９（中央理化工業（株））等が挙げられる。 The resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a modified product thereof, or a commercially available product may be used. Examples of emulsions of resins having structural units derived from α-olefins having 2 to 20 carbon atoms and modified products thereof include Arrow Base (registered trademark) SA-1200, SB-1200, SE-1200, SB-1010 (Unitika). ), Aptolock (registered trademark) BW-5550 (Mitsubishi Chemical Corporation), Auroren (registered trademark) AE-202, AE-301 (Nippon Paper Industries Co., Ltd.), Aquatex (registered trademark) EC -1200, EC-1700, AC-3100, MC-4400, HA-1100, 909 (Chuo Rika Kogyo Co., Ltd.).
　塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂としては、例えば、エラスレン（登録商標）４０１Ａ、３０３Ｂ（昭和電工（株））、ハードレン（登録商標）ＣＹ－９１２２Ｐ、ＣＹ－９１２４Ｐ、ＨＭ－２１Ｐ、Ｍ－２８Ｐ、Ｆ－２Ｐ、Ｆ－６Ｐ、Ｆ－６９、１３－ＬＰ、１３－ＬＬＰ、１４－ＬＷＰ、１４－ＷＬ－Ｐ、１５－ＬＰ、１５－ＬＬＰ、１６－ＬＰ、ＤＸ－５２６Ｐ、ＤＸ－５３０ＰおよびＢＳ－４０（東洋紡（株））、並びに、スーパークロン（登録商標）８０３Ｌ、８０３ＭＷ、８１４ＨＳ、３９０Ｓ、ＨＥ－３０５、ＨＥ－５０５、ＨＥ－５１０、ＨＥ－５１５、ＨＥ－９１０、ＨＥ－９１５、ＨＥ－１０７０、ＨＥ－１２００、ＨＰ－２０５、ＨＰ－２１５およびＨＰ－６２０（日本製紙ケミカル（株））等が挙げられる。 Examples of the resin having a structural unit derived from a chlorinated α-olefin having 2 to 20 carbon atoms include Eraslene (registered trademark) 401A, 303B (Showa Denko KK), Harden (registered trademark) CY-9122P, CY-9124P, HM-21P, M-28P, F-2P, F-6P, F-69, 13-LP, 13-LLP, 14-LWP, 14-WL-P, 15-LP, 15-LLP, 16-LP, DX-526P, DX-530P and BS-40 (Toyobo Co., Ltd.), and Supercron (registered trademark) 803L, 803MW, 814HS, 390S, HE-305, HE-505, HE-510, HE-515, HE-910, HE-915, HE-1070, HE-1200, HP-205, HP-215 and HP-620 (made in Japan) Chemicals Co., Ltd.), and the like.
　塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂は、エマルションの形態であってもよい。このようなエマルションは、塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂を乳化することによって製造してもよいし、市販のものを用いてもよい。塩素化された炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂のエマルションとしては、例えば、ハードレン（登録商標）ＥＷ－５３０３、ＥＨ－８０１、ＥＷ－５５０４、ＥＺ－１０００およびＥＺ－２０００（東洋紡（株））、スーパークロン（登録商標）Ｅ－６０４、Ｅ－４８０ＴおよびＥ－４１５（日本製紙ケミカル（株））等が挙げられる。 The resin having a chlorinated α-olefin derived structural unit having 2 to 20 carbon atoms may be in the form of an emulsion. Such an emulsion may be produced by emulsifying a chlorinated resin having a structural unit derived from an α-olefin having 2 to 20 carbon atoms, or a commercially available product may be used. Examples of emulsions of resins having structural units derived from chlorinated α-olefins having 2 to 20 carbon atoms include, for example, HARDLEN® EW-5303, EH-801, EW-5504, EZ-1000 and EZ- 2000 (Toyobo Co., Ltd.), Supercron (registered trademark) E-604, E-480T and E-415 (Nippon Paper Chemical Co., Ltd.).
　ポリウレタンは、発泡ポリウレタンでもよく、非発泡ポリウレタンでもよいが、好ましくは非発泡ポリウレタンである。非発泡ポリウレタンの中でも、水溶性または水分散性ポリウレタンが好ましい。ポリウレタンは、市販のものを用いることができる。市販のポリウレタンとしては、例えば、ニッポラン（登録商標）３１１０、３１１６、３０１６、３１１３、３１２４、３１２６、３２３０（日本ポリウレタン工業（株））等が挙げられる。市販の水溶性または水分散性ポリウレタンとしては、例えば、ディスパコール（登録商標）Ｕ－４２、Ｕ－５３、Ｕ－５４、Ｕ－５６、ＫＡ－８４８１、ＫＡ－８５８４、ＫＡ－８７５５、ＫＡ－８７５６およびＫＡ－８７６６（住友コベストロウレタン（株））、ハイドラン（登録商標）ＨＷ－１１１、ＨＷ－３１１、ＨＷ－３３３、ＨＷ－３５０、ＨＷ－３３７、ＨＷ－３７４、ＡＰ－２０、ＡＰ－６０ＬＭおよびＡＰ－８０（ＤＩＣ（株））、ユープレン（登録商標）ＵＸＡ-３０６、ＵＸＡ-３０７、パーマリンＵＡ－１５０、パーマリンＵＡ－２００、パーマリンＵＡ－３００、パーマリンＵＡ－３１０およびユーコートＵＷＳ－１４５（三洋化成工業（株））、スーパーフレックス（登録商標）１０７Ｍ、１１０、１２６、１３０、１５０、１６０、２１０、３００、３６１、３７０、４１０、４２０、４６０、５００Ｍ、７００、７５０、８２０および８６０（第一工業製薬（株））、並びにアデカボンタイター（登録商標）ＨＵＸ－４０１、ＨＵＸ－４２０Ａ、ＨＵＸ－３８０、ＨＵＸ－５６１、ＨＵＸ－２１０、ＨＵＸ－８２２、ＨＵＸ－８９５およびＨＵＸ－８３０（（株）ＡＤＥＫＡ）等が挙げられる。 The polyurethane may be foamed polyurethane or non-foamed polyurethane, but is preferably non-foamed polyurethane. Among non-foamed polyurethanes, water-soluble or water-dispersible polyurethanes are preferable. A commercially available polyurethane can be used. Examples of commercially available polyurethanes include Nipponan (registered trademark) 3110, 3116, 3016, 3113, 3124, 3126, 3230 (Nippon Polyurethane Industry Co., Ltd.). Commercially available water-soluble or water-dispersible polyurethanes include, for example, Dispacol (registered trademark) U-42, U-53, U-54, U-56, KA-8484, KA-8484, KA-8755, KA- 8756 and KA-8766 (Sumitomo Covestrourethane Co., Ltd.), Hydran (registered trademark) HW-111, HW-311, HW-333, HW-350, HW-337, HW-374, AP-20, AP- 60LM and AP-80 (DIC Corporation), Uprene (registered trademark) UXA-306, UXA-307, Permarin UA-150, Permarin UA-200, Permarin UA-300, Permarin UA-310 and Ucourt UWS-145 ( Sanyo Chemical Industries, Ltd.), Superflex (registered trademark) 107M, 110, 126, 130 150, 160, 210, 300, 361, 370, 410, 420, 460, 500M, 700, 750, 820 and 860 (Daiichi Kogyo Seiyaku Co., Ltd.), and Adekabon Titer (registered trademark) HUX-401, HUX -420A, HUX-380, HUX-561, HUX-210, HUX-822, HUX-895 and HUX-830 (Adeka Co., Ltd.).
　ポリ塩化ビニルは、塩化ビニルを懸濁重合または塊状重合する方法等で得られる。ポリ塩化ビニルとしては、例えば、硬質ポリ塩化ビニル、半硬質ポリ塩化ビニル、軟質ポリ塩化ビニル等が挙げられる。好ましくは、軟質ポリ塩化ビニルである。ポリ塩化ビニルは、例えば、カネビニールＳ－４００、ＰＳＨ－１８０、ＰＳＬ－１８０（（株）カネカ）等が挙げられる。ポリ塩化ビニルのエマルションとしては、例えば、ビニブラン７０１、７００、７１１（日信化学工業（株））等が挙げられる。 Polyvinyl chloride is obtained by a method such as suspension polymerization or bulk polymerization of vinyl chloride. Examples of the polyvinyl chloride include hard polyvinyl chloride, semi-rigid polyvinyl chloride, and soft polyvinyl chloride. Preferably, it is soft polyvinyl chloride. Examples of the polyvinyl chloride include Kanevinyl S-400, PSH-180, PSL-180 (Kaneka Corporation), and the like. Examples of the polyvinyl chloride emulsion include Vinibrand 701, 700, and 711 (Nisshin Chemical Industry Co., Ltd.).
　塩素化ポリ塩化ビニルとは、ポリ塩化ビニルを、気相または液相等の塩素化方法によって塩素化したものである。ポリ塩化ビニルとしては、例えば、塩化ビニルの単独重合体および塩化ビニルと他の単量体との共重合体が挙げられる。他の単量体としては、例えば、エチレン、プロピレン、アルキルビニルエーテル、ビニリデンクロライド、酢酸ビニル、アクリル酸エステル、およびマレイン酸エステル等が挙げられる。塩素化ポリ塩化ビニルは、例えば、セキスイＰＶＣ－ＨＡ（積水化学工業（株））等が挙げられる。 Chlorinated polyvinyl chloride is obtained by chlorinating polyvinyl chloride by a chlorination method such as a gas phase or a liquid phase. Examples of polyvinyl chloride include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and other monomers. Examples of other monomers include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, and maleic acid ester. Examples of the chlorinated polyvinyl chloride include Sekisui PVC-HA (Sekisui Chemical Co., Ltd.).
　ポリ塩化ビニリデンとしては、例えば、サラン（ＳＡＲＡＮ）Ｘ０５２５３－１６（ダウ・ケミカル社製）、サランラップ（登録商標）用樹脂（旭化成社製）等が挙げられる。ポリ塩化ビニリデンのエマルションとしては、例えば、Ｄｉｏｆａｎ １９３Ｄ、Ａ７３６、Ａ０３６、Ａ０５０、Ａ０６３、Ｂ２０４、Ａ１１５（ソルベイ社製）等が挙げられる。 Examples of the polyvinylidene chloride include SARAN X05253-16 (manufactured by Dow Chemical Co., Ltd.), Saran Wrap (registered trademark) resin (manufactured by Asahi Kasei Co., Ltd.), and the like. Examples of the polyvinylidene chloride emulsion include Diofan 193D, A736, A036, A050, A063, B204, A115 (manufactured by Solvay).
　塩化ビニル－塩化ビニリデン共重合体としては、例えば、ＩＸＡＮ　ＳＧＡ－１（ソルベイ社製）等が挙げられる。 Examples of the vinyl chloride-vinylidene chloride copolymer include IXAN SGA-1 (manufactured by Solvay).
　塩化ビニリデン－（メタ）アクリル酸エステル共重合体としては、例えば、ＩＸＡＮ　ＰＶＳ－１０９、８０１、８１５、Ｄｉｏｆａｎ Ａ５８６、Ａ６０２、Ａ６１０（ソルベイ社製）等が挙げられる。 Examples of the vinylidene chloride- (meth) acrylic acid ester copolymer include IXAN PVS-109, 801, 815, Diofan A586, A602, A610 (manufactured by Solvay).
　クロロプレン系樹脂は、クロロプレンの単独重合体、またはクロロプレンと他の単量体との共重合体である。他の単量体としては、例えば、イソプレン、ブタジエン、ジクロロブタジエン、スチレン、アクリロニトリル、アクリル酸エステル、メタクリル酸エステル、アクリル酸、メタクリル酸、イタコン酸等が挙げられる。 The chloroprene resin is a chloroprene homopolymer or a copolymer of chloroprene and other monomers. Examples of the other monomer include isoprene, butadiene, dichlorobutadiene, styrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, itaconic acid, and the like.
　酸変性クロロプレン系樹脂は、上記クロロプレン系樹脂に、α，β－不飽和カルボン酸およびその無水物から選ばれる少なくとも１種をグラフト共重合することで得られる。α，β－不飽和カルボン酸およびその酸無水物としては、例えば、炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂の変性物として例示したものが挙げられる。 The acid-modified chloroprene resin is obtained by graft copolymerizing the chloroprene resin with at least one selected from α, β-unsaturated carboxylic acids and anhydrides thereof. Examples of α, β-unsaturated carboxylic acids and acid anhydrides thereof include those exemplified as modified products of resins having structural units derived from α-olefins having 2 to 20 carbon atoms.
　クロロプレン系樹脂および酸変性クロロプレン系樹脂としては、例えば、スカイプレン（登録商標）Ｇ－４２、Ｇ－４０Ｓ、Ｇ－５５、Ｇ－４０、Ｓ－１、Ｇ－４０Ｔ、Ｂ－３０Ｓ、Ｙ－３１（東ソー（株））、ショウプレン（登録商標）Ｗ、ＡＦ、ＷＨＶ、ＷＸＪ、ＷＢ（昭和電工（株））、並びにデンカクロロプレン（登録商標）Ａ－３０、Ａ－７０、Ａ－９０、Ａ－９１、Ｍ－１３０Ｌ、ＤＣＲ－１１（デンカ（株））等が挙げられる。クロロプレン系樹脂および酸変性クロロプレン系樹脂のエマルションとしては、例えば、スカイプレン（登録商標）ＧＦＬ－８２０、ＧＦＬ－８９０、ＧＦＬ－２８０、ＬＡ－５０２、ＬＡ－６６０、ＳＬ－３６０、ＳＬ－３９０およびＳＬ－５９０（東ソー（株））、ショウプレン（登録商標）１１５、５７１、５７２、６５０、６７１Ａ、７５０、ＳＤ７８およびＳＤ７７Ｓ（昭和電工（株））、並びにデンカクロロプレン（登録商標）ＬＡ－５０およびＬＣ－５０１（デンカ（株））等が挙げられる。 Examples of the chloroprene resin and the acid-modified chloroprene resin include Skyprene (registered trademark) G-42, G-40S, G-55, G-40, S-1, G-40T, B-30S, Y- 31 (Tosoh Corp.), Shoprene (Registered Trademark) W, AF, WHV, WXJ, WB (Showa Denko Co., Ltd.), and Denka Chloroprene (Registered Trademark) A-30, A-70, A-90, A -91, M-130L, DCR-11 (Denka Co., Ltd.) and the like. Examples of emulsions of chloroprene resin and acid-modified chloroprene resin include Skyprene (registered trademark) GFL-820, GFL-890, GFL-280, LA-502, LA-660, SL-360, SL-390 and SL-590 (Tosoh Corporation), Shoprene (registered trademark) 115, 571, 572, 650, 671A, 750, SD78 and SD77S (Showa Denko), and Denkachloroprene (registered trademark) LA-50 and LC -501 (Denka Co., Ltd.).
　臭素化ブチルゴムとしては、例えば、ＪＳＲ ＢＲＯＭＯＢＵＴＹＬ ２２５５、２２４４（ＪＳＲ社）、エクソンブロモブチル２２５５（エクソンモービルケミカル社）等が挙げられる。 Examples of the brominated butyl rubber include JSR BROMOBUTYL 2255, 2244 (JSR), Exxon Bromobutyl 2255 (ExxonMobil Chemical).
　変性ゴムとしては、例えばイソモノオレフィンとパラメチルスチレンとの共重合体の塩素化または臭素化変性共重合体が挙げられ、市販品としては、例えば、Ｅｘｐｒｏ５０（エクソン社）が挙げられる。 Examples of the modified rubber include a chlorinated or brominated modified copolymer of a copolymer of isomonoolefin and paramethylstyrene, and examples of commercially available products include Expro 50 (Exxon).
　スチレン系ブロック共重合体としては、例えば、ジエンブロックとスチレンブロックからなるブロック共重合体が挙げられる。具体的には、スチレン－ブタジエンブロック共重合体（ＳＢ）、スチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－ブタジエン－ブチレン－スチレン共重合体（ＳＢＢＳ）若しくはそれらブロック共重合体の水素添加物、スチレン・イソブチレン－スチレントリブロック共重合体（ＳＩＢＳ）、スチレン－イソブチレンジブロック共重合体（ＳＩＢ）が挙げられる。このような水素添加物は、スチレンブロックとジエンブロックの全てが水素添加されたブロック共重合体であっても、ジエンブロックのみ水素添加されたブロック共重合体あるいはスチレンブロックとジエンブロックの一部が水素添加されたブロック共重合体等の部分水素添加物であってもよい。 Examples of the styrene block copolymer include a block copolymer composed of a diene block and a styrene block. Specifically, styrene-butadiene block copolymer (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-butylene-styrene copolymer. Examples thereof include a polymer (SBBS) or a hydrogenated product of these block copolymers, a styrene / isobutylene-styrene triblock copolymer (SIBS), and a styrene-isobutylene diblock copolymer (SIB). Such a hydrogenated product is a block copolymer in which all of the styrene block and the diene block are hydrogenated, or a block copolymer in which only the diene block is hydrogenated or a part of the styrene block and the diene block. It may be a partially hydrogenated product such as a hydrogenated block copolymer.
　分散液の安定性をより高めるために、本発明の分散液は、他の樹脂として、ポリビニルアルコール、ポリアクリル酸ナトリウム、カルボキシメチルセルロースおよびヒドロキシエチルセルロース等の水溶性樹脂を含有していてもよい。 In order to further improve the stability of the dispersion, the dispersion of the present invention may contain a water-soluble resin such as polyvinyl alcohol, sodium polyacrylate, carboxymethyl cellulose, and hydroxyethyl cellulose as another resin.
　本発明の分散液は、他の樹脂として、粘着付与樹脂を含有していてもよい。このような樹脂としては、例えば、ロジン類、テルペン系樹脂、炭素数５の石油留分を重合した石油系樹脂およびこの水素添加樹脂、炭素数９の石油留分を重合した石油系樹脂およびこの水素添加樹脂、その他の石油系樹脂、クマロン樹脂並びにインデン樹脂等が挙げられる。具体的には、例えば、ロジン、重合ロジン、不均化ロジン、水添ロジン、マレイン化ロジン、フマル化ロジンおよびこれらのグリセリンエステル、ペンタエリスリトールエステル、メチルエステル、トリエチレングリコールエステル、フェノール変性物およびそのエステル化物等のロジン類；テルペン重合体、テルペンフェノール、β－ピネン重合体、芳香族変性テルペン重合体、α－ピネン重合体、テルペン系水素添加樹脂等のテルペン系樹脂；炭素数５の石油留分を重合した石油系樹脂、炭素数９の石油留分を重合した石油系樹脂およびこれらの水素添加樹脂；マレイン酸変性物並びにフマル酸変性物等の石油系樹脂、塩素化パラフィン等が挙げられる。 The dispersion of the present invention may contain a tackifying resin as another resin. Examples of such resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and Examples thereof include hydrogenated resins, other petroleum resins, coumarone resins, and indene resins. Specifically, for example, rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin and their glycerin ester, pentaerythritol ester, methyl ester, triethylene glycol ester, phenol modified product and Rosins such as esterified products; terpene polymers such as terpene polymers, terpene phenols, β-pinene polymers, aromatic modified terpene polymers, α-pinene polymers, terpene hydrogenated resins, etc .; petroleum having 5 carbon atoms Petroleum resins obtained by polymerizing fractions, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms and their hydrogenated resins; petroleum resins such as maleic acid-modified products and fumaric acid-modified products, chlorinated paraffins, etc. It is done.
　テルペン系樹脂としては、例えば、ＹＳレジンＰＸ、ＰＸＮ、ＹＳポリスター、マイティエース、ＹＳレジンＴＯ、ＴＲおよびクリアロンＰ、Ｍ、Ｋ（ヤスハラケミカル（株））、タマノル８０３Ｌ、９０１（荒川化学工業（株））並びに、テルタック８０（日本テルペン化学（株））等が挙げられる。テルペン系樹脂のエマルションとしては、例えば、タマノルＥ－２００ＮＴ、Ｅ１００（荒川化学工業（株））等が挙げられる。 Examples of terpene resins include YS Resin PX, PXN, YS Polyster, Mighty Ace, YS Resin TO, TR and Clearon P, M, K (Yasuhara Chemical Co., Ltd.), Tamanoru 803L, 901 (Arakawa Chemical Industries, Ltd.) ) And Tertac 80 (Nippon Terpene Chemical Co., Ltd.). Examples of the terpene resin emulsion include Tamorol E-200NT and E100 (Arakawa Chemical Industries, Ltd.).
　塩素化パラフィンとしては、例えば、エンパラ（登録商標）７０、５０、ＡＲ－５００（味の素ファインテクノ（株））、トヨパラックス（登録商標）２５０、２６５、２７０、１５０、Ａ５０（東ソー（株））等が挙げられる。 Examples of the chlorinated paraffin include Enpara (registered trademark) 70, 50, AR-500 (Ajinomoto Fine Techno Co., Ltd.), Toyoparax (registered trademark) 250, 265, 270, 150, A50 (Tosoh Corp.), etc. Is mentioned.
　本発明の分散液が他の樹脂またはゴムを含む場合、その量は、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、好ましくは０．０１重量部以上であり、好ましくは１００重量部以下、より好ましくは５０重量部以下、さらに好ましくは３０重量部以下、さらに一層好ましくは２０重量部以下である。 When the dispersion of the present invention contains other resin or rubber, the amount thereof is preferably 0.01 parts by weight or more, preferably 100 parts by weight or more, based on the total of 100 parts by weight of the chlorinated rubber and the compound having a polymerizable group. Is 100 parts by weight or less, more preferably 50 parts by weight or less, still more preferably 30 parts by weight or less, and still more preferably 20 parts by weight or less.
＜増粘剤＞
　増粘剤は、分散液の粘性調整のために使用することができる。増粘剤としては、例えば、アデカノール（登録商標）ＵＨ－１４０Ｓ、ＵＨ－４２０、ＵＨ－４３８、ＵＨ－４５０ＶＦ、ＵＨ－４６２、ＵＨ－４７２、ＵＨ－５２６、ＵＨ－５３０、ＵＨ－５４０、ＵＨ－５４１ＶＦ、ＵＨ－５５０、ＵＨ－７５２およびＨ－７５６ＶＦ（（株）ＡＤＥＫＡ）、並びにＳＮシックナー９２０、９２２、９２４、９２６、９２９－Ｓ、Ａ－８０１、Ａ－８０６、Ａ－８１２、Ａ－８１３、Ａ－８１８、６２１Ｎ、６３６、６０１、６０３、６１２、６１３、６１５、６１８、６２１Ｎ、６３０、６３４、６３６および４０５０（サンノプコ（株））等が挙げられる。 <Thickener>
A thickener can be used to adjust the viscosity of the dispersion. Examples of the thickener include Adecanol (registered trademark) UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH -541VF, UH-550, UH-752 and H-756VF (ADEKA), and SN thickeners 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A- 813, A-818, 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, and 4050 (San Nopco).
＜分散液の製造方法＞
　本発明の分散液は、後述の実施例に記載するような方法によって製造することができる。以下、本発明の分散液の製造方法を詳しく説明する。 <Method for producing dispersion>
The dispersion of the present invention can be produced by a method as described in the examples below. Hereafter, the manufacturing method of the dispersion liquid of this invention is demonstrated in detail.
　水、塩素化ゴムおよび重合性基を有する化合物、および必要に応じて他の成分（特に、界面活性剤等）を混合および撹拌して、予備分散液を調製する。この予備分散の方法に特に限定はなく、公知の手段および装置を使用して行うことができる。公知の装置としては、例えば、ホモミキサーが挙げられる。ホモミキサーを使用する場合、その撹拌数は、好ましくは５，０００～２０，０００ｒｐｍ、より好ましくは８，０００～２０，０００ｒｐｍであり、撹拌時間は、好ましくは２～１０分、より好ましくは３～１０分である。室温である混合物を用いて、撹拌を開始することが好ましい。 Water, a chlorinated rubber, a compound having a polymerizable group, and other components (particularly, a surfactant, etc.) are mixed and stirred as necessary to prepare a preliminary dispersion. The preliminary dispersion method is not particularly limited, and can be performed using known means and apparatuses. Examples of known devices include a homomixer. When a homomixer is used, the number of stirring is preferably 5,000 to 20,000 rpm, more preferably 8,000 to 20,000 rpm, and the stirring time is preferably 2 to 10 minutes, more preferably 3 ~ 10 minutes. It is preferred to start stirring with the mixture at room temperature.
　次いで、高圧ホモジナイザーを用いて、得られた予備分散液の均質化処理を行う。高圧ホモジナイザーの圧力は、好ましくは４０～１，０００ｂａｒ、より好ましくは４０～８００ｂａｒである。前記圧力が４０ｂａｒより小さいと、分散質の微分散化が不充分になり、逆に前記圧力が１，０００ｂａｒを超えても、分散質の微分散化は向上しない。高圧ホモジナイザーによる均質化処理の回数は、好ましくは２～１０回、より好ましく３～８回である。前記処理の回数が２回よりも少ないと、分散質の微分散化が不充分になり、逆に前記処理の回数が１０回を超えても、分散質の微分散化は向上しない。ホモミキサーにより得られた予備分散液を室温まで冷却してから、高圧ホモジナイザーによる均質化処理を開始することが好ましい。 Next, the obtained preliminary dispersion is homogenized using a high-pressure homogenizer. The pressure of the high-pressure homogenizer is preferably 40 to 1,000 bar, more preferably 40 to 800 bar. If the pressure is less than 40 bar, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the pressure exceeds 1,000 bar, fine dispersion of the dispersoid is not improved. The number of homogenization treatments with a high-pressure homogenizer is preferably 2 to 10 times, more preferably 3 to 8 times. If the number of treatments is less than two, fine dispersion of the dispersoid becomes insufficient. Conversely, even if the number of treatments exceeds 10, the fine dispersion of the dispersoid is not improved. It is preferable to start the homogenization process by a high-pressure homogenizer after cooling the preliminary dispersion obtained by the homomixer to room temperature.
　高圧ホモジナイザーとしては、例えば、（株）エスエムテー製の「ＬＡＢ１０００」、「ＬＡＢ２０００」、「１５ＭＲ」、「Ｇ－ＭＯＤＥＬ」、「Ｒ－ＭＯＤＥＬ」等が挙げられる。 Examples of the high-pressure homogenizer include “LAB1000”, “LAB2000”, “15MR”, “G-MODEL”, “R-MODEL” manufactured by SMT Co., Ltd., and the like.
　上記のようにして製造した本発明の分散液に、さらに水を添加し、撹拌して、希釈した分散液を製造してもよい。また、上記のようにして製造した本発明の分散液に、さらに他の成分（例えば、レベリング剤）を添加し、撹拌して、他の成分を含有する分散液を製造してもよい。 A diluted dispersion may be produced by adding water to the dispersion of the invention produced as described above and stirring. Moreover, you may add the other component (for example, leveling agent) to the dispersion liquid of this invention manufactured as mentioned above, and stir, and may manufacture the dispersion liquid containing another component.
＜分散液の使用＞
　本発明の分散液は、上述したように、水系接着剤、プライマーまたはそれらの原料として有用である。また、本発明は、前記分散液から形成される塗膜、および前記塗膜の硬化物を提供する。また、本発明は、第１の基材と、前記硬化物と、接着剤層と、第２の基材とが、この順に積層されている積層体を提供する。第１の基材は、オレフィン系重合体またはエチレン－酢酸ビニル共重合体からなることが好ましい。本発明の積層体において、接着剤層と第２の基材との間に、さらに前記硬化物が存在していてもよい。 <Use of dispersion>
As described above, the dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof. Moreover, this invention provides the coating film formed from the said dispersion liquid, and the hardened | cured material of the said coating film. Moreover, this invention provides the laminated body by which the 1st base material, the said hardened | cured material, the adhesive bond layer, and the 2nd base material are laminated | stacked in this order. The first substrate is preferably made of an olefin polymer or an ethylene-vinyl acetate copolymer. In the laminate of the present invention, the cured product may further exist between the adhesive layer and the second substrate.
　本発明の分散液を塗布する被着体、または本発明の塗膜および硬化物を積層させる被着体（第１の基材および第２の基材を含む）の材料としては、例えば、木材、合板、中密度繊維板（ＭＤＦ）、パーティクルボード、ファイバーボード等の木質系材料；綿布、綿含有繊維、麻布、レーヨン等のセルロース系材料；（１）エチレンの単独重合体および共重合体、プロピレンの単独重合体および共重合体等のオレフィン系重合体、（２）スチレンの単独重合体および共重合体、（３）ポリカーボネート、（４）アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、（５）ポリ（メタ）アクリル樹脂、（６）ポリエステル、（７）ポリエーテル、（８）ポリ塩化ビニル、（９）発泡または非発泡のポリウレタン、（１０）発泡または未発泡のエチレン－酢酸ビニル共重合体（ＥＶＡ）、（１１）ポリアミド６、ポリアミドイロン６６等の発泡または未発泡のポリアミド系樹脂等のプラスチック材料；ゴム；ポリアミノ酸；天然皮革；合成皮革；ガラス、陶磁器等のセラミック材料；および鉄、ステンレス、銅、アルミニウム等の金属材料等が挙げられる。被着体は、１種の材料からなるものでもよく、２種以上の材料からなるものでもよい。また、被着体は、前記プラスチック材料と、タルク、シリカ、活性炭、炭素繊維等の充填剤との混練成形品であってもよい。 Examples of the material of the adherend to which the dispersion liquid of the present invention is applied, or the adherend (including the first base material and the second base material) on which the coating film and the cured product of the present invention are laminated include wood. Wood materials such as plywood, medium density fiberboard (MDF), particle board, fiber board; cellulose materials such as cotton cloth, cotton-containing fibers, linen, rayon; (1) homopolymers and copolymers of ethylene; Olefin-based polymers such as propylene homopolymer and copolymer, (2) styrene homopolymer and copolymer, (3) polycarbonate, (4) acrylonitrile-butadiene-styrene copolymer (ABS resin), (5) Poly (meth) acrylic resin, (6) Polyester, (7) Polyether, (8) Polyvinyl chloride, (9) Foamed or non-foamed polyurethane, (10) Foamed Is an unfoamed ethylene-vinyl acetate copolymer (EVA), (11) a plastic material such as a foamed or unfoamed polyamide-based resin such as polyamide 6 and polyamideylon 66; rubber; polyamino acid; natural leather; synthetic leather; Examples thereof include ceramic materials such as glass and ceramics; and metal materials such as iron, stainless steel, copper, and aluminum. The adherend may be made of one kind of material or may be made of two or more kinds of materials. The adherend may be a kneaded molded product of the plastic material and a filler such as talc, silica, activated carbon, or carbon fiber.
　本発明の分散液は、前記被着体の中でも、セルロース系材料とプラスチック材料との接着、ポリ塩化ビニル、エチレン－酢酸ビニル共重合体、綿含有繊維、ポリアミド系樹脂、オレフィン系重合体、ポリウレタン、ゴムまたは架橋ゴム、および合成皮革等の接着に好適に使用することができる。これら被着体の形状としては、例えば、フィルム、シートおよびブロック状等が挙げられるが、好ましくは、フィルムまたはシートの形状の被着体が好ましい。 Among the adherends, the dispersion liquid of the present invention includes adhesion between cellulosic material and plastic material, polyvinyl chloride, ethylene-vinyl acetate copolymer, cotton-containing fiber, polyamide resin, olefin polymer, polyurethane. , Rubber or cross-linked rubber, and synthetic leather can be suitably used for adhesion. Examples of the shape of the adherend include a film, a sheet, and a block shape, and an adherend having a film or sheet shape is preferable.
　オレフィン系重合体としては、例えば、＜他の樹脂またはゴム＞で説明した炭素数２～２０のα－オレフィン由来の構造単位を有する樹脂および変性物等が挙げられる。また、プラスチック材料としては、例えば、＜他の樹脂またはゴム＞で説明したものが挙げられる。 Examples of the olefin polymer include resins having a structural unit derived from an α-olefin having 2 to 20 carbon atoms described in <Other resin or rubber> and modified products. Moreover, as a plastic material, what was demonstrated by <other resin or rubber> is mentioned, for example.
　綿含有繊維は、綿１００％の繊維であってもよいし、綿と、他の天然繊維および／または化学繊維との混紡繊維であってもよい。他の天然繊維としては、例えば、羊毛、絹および麻等が挙げられる。化学繊維としては、例えば、合成繊維（例えば、ポリエステル系繊維、ポリアミド系繊維）、半合成繊維（例えば、アセテート等のセルロース系繊維、プロミックス等のタンパク質系繊維）、再生繊維（例えば、レーヨン、キュプラ、ポリノジック等のセルロース系繊維）および無機繊維（例えば、炭素繊維、ガラス繊維）等が挙げられる。綿含有繊維の形状としては、例えば、織物、編物、不織布、メリヤス、フェルト、フィルムまたはブロック状等が挙げられる。 Cotton-containing fibers may be 100% cotton fibers, or may be blended fibers of cotton and other natural fibers and / or chemical fibers. Examples of other natural fibers include wool, silk and hemp. Examples of chemical fibers include synthetic fibers (for example, polyester fibers and polyamide fibers), semi-synthetic fibers (for example, cellulose fibers such as acetate, protein fibers such as promix), and regenerated fibers (for example, rayon, And cellulose fibers such as cupra and polynosic) and inorganic fibers (for example, carbon fibers and glass fibers). Examples of the shape of the cotton-containing fiber include woven fabric, knitted fabric, nonwoven fabric, knitted fabric, felt, film, and block shape.
　ポリアミド系樹脂としては、例えば、ポリアミド６、ポリアミド６，６、ポリアミド４，６、ポリアミド１１およびポリアミド１２等が挙げられる。ポリアミド系樹脂の形状は、フィルム、ブロック、繊維または発泡体状等のいずれでもよい。 Examples of the polyamide-based resin include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11 and polyamide 12. The shape of the polyamide resin may be any of a film, a block, a fiber, or a foam.
　ゴムまたは架橋ゴムとしては、例えば、熱可塑性ゴム；天然ゴム、イソプレンゴム、ブタジエンゴム、スチレン－ブタジエンゴム、イソプレンゴム、アクロニトリル－ブタジエンゴム、クロロプレンゴム等のジエン系ゴム；ブチルゴム、エチレン－プロピレンゴム、エチレン－プロピレン－ジエンゴム、シリコーンゴム、フッ素ゴム等の非ジエン系ゴム；およびこれらの架橋物が挙げられる。ゴムはまたは架橋ゴムは、それぞれ単独で用いてもよいし、また２種以上併用してもよい。必要に応じて、クレー、カーボンブラックまたはシリカ等の補強剤、シランカップリング剤、老化防止剤、軟化剤、亜鉛華、ステアリン酸、加硫促進剤、加硫剤、硫黄等を併用してもよい。 Examples of rubber or cross-linked rubber include thermoplastic rubbers; natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, chloroprene rubber and other diene rubbers; butyl rubber, ethylene-propylene rubber And non-diene rubbers such as ethylene-propylene-diene rubber, silicone rubber and fluororubber; and cross-linked products thereof. The rubber or the crosslinked rubber may be used alone or in combination of two or more. If necessary, reinforcing agents such as clay, carbon black or silica, silane coupling agents, anti-aging agents, softeners, zinc white, stearic acid, vulcanization accelerators, vulcanizing agents, sulfur, etc. may be used in combination. Good.
　合成皮革とは、狭義の合成皮革と人工皮革との双方を含む。つまり、合成皮革は、天然または合成の布地等に合成樹脂を塗布して得られる合成皮革でもよく、マイクロファイバー等の布地（通常、不織布）に合成樹脂を含浸して得られる人工皮革でもよく、マイクロファイバー等の布地（通常、不織布）に合成樹脂を含浸し、さらに合成樹脂を塗布して得られる人工皮革でもよい。これらの合成樹脂としては、例えば、ポリウレタン系樹脂、ポリアミド系樹脂およびポリアミノ酸系樹脂等が挙げられ、好ましくは、ポリウレタン系樹脂である。 Synthetic leather includes both synthetic leather and artificial leather in the narrow sense. That is, the synthetic leather may be a synthetic leather obtained by applying a synthetic resin to a natural or synthetic fabric or the like, or may be an artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber, Artificial leather obtained by impregnating a synthetic resin into a fabric (usually a nonwoven fabric) such as microfiber and further applying the synthetic resin may be used. Examples of these synthetic resins include polyurethane resins, polyamide resins, polyamino acid resins, and the like, and polyurethane resins are preferable.
　本発明の分散液は、フィルム、シート、構造材料、建築材料、自動車部品、電気・電子製品、包装材料、衣料および靴等の被着体の接着に有効に使用することができる。特に、本発明の分散液は、スポーツシューズ、タウンシューズ、ビジネスシューズ等の紳士靴、婦人靴、および工業用の作業靴等の履物における、胛被、中底、外底等の構成材料（被着体）を接着するための接着剤、プライマーまたはそれらの原料として好適である。これらの被着体の表面は、平滑であってもよいし、凹凸を有していてもよい。また、接着性を高めるために、被着体に表面処理を施してもよい。表面処理としては、例えば、プライマー処理、ブラスト処理、薬品処理、脱脂、火炎処理、酸化処理、蒸気処理、コロナ放電処理、紫外線照射処理、プラズマ処理、イオン処理、アンカー層の形成などが挙げられる。 The dispersion of the present invention can be used effectively for adhesion of adherends such as films, sheets, structural materials, building materials, automobile parts, electrical / electronic products, packaging materials, clothing and shoes. In particular, the dispersion liquid of the present invention is used for constituting materials (covers) such as a hood, an insole, and an outer bottom in footwear such as men's shoes such as sports shoes, town shoes, and business shoes, women's shoes, and industrial work shoes. It is suitable as an adhesive, a primer or a raw material thereof for adhering the body. The surface of these adherends may be smooth or may have irregularities. Moreover, in order to improve adhesiveness, you may surface-treat to a to-be-adhered body. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and anchor layer formation.
　次に、上述した本発明の積層体の製造方法について説明する。
　まず、第１の基材、任意に第２の基材の表面に分散液を塗布する。塗布は、公知の方法で行えばよい。公知の方法としては、例えば、グラビアロールコーティング、リバースロールコーティング、バーコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗りおよびへら塗り等が挙げられる。 Next, the manufacturing method of the laminated body of this invention mentioned above is demonstrated.
First, the dispersion is applied to the surface of the first substrate, optionally the second substrate. Application may be performed by a known method. Known methods include, for example, gravure roll coating, reverse roll coating, bar coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brushing and spatula coating.
　分散液の塗布および乾燥は、それぞれ１回のみ行なってもよいし、２回以上行なってもよい。塗布および乾燥の方法は、それぞれ同じ方法を組み合わせてもよいし、異なる方法を組み合わせてもよい。 The application and drying of the dispersion may be performed only once, or may be performed twice or more. The application and drying methods may be combined with each other, or different methods may be combined.
　第１の基材へ分散液を塗布した後、塗膜の乾燥または加熱処理を行なってもよいし、さらに、その後に電磁波を照射してもよい。加熱温度は、例えば３０～１５０℃程度、好ましくは４０～８０℃程度である。加熱時間は、例えば１秒～１時間程度、好ましくは５秒～３０分間程度、より好ましくは５秒～１０分間程度である。塗膜の乾燥または加熱処理の前後に、さらに、塗膜の放置（自然乾燥）を行なってもよい。分散液から形成された塗膜に電磁線（特に、紫外線）を照射して、塗膜の硬化物を形成することが好ましい。 After applying the dispersion liquid to the first substrate, the coating film may be dried or heat-treated, and then electromagnetic waves may be irradiated. The heating temperature is, for example, about 30 to 150 ° C., preferably about 40 to 80 ° C. The heating time is, for example, about 1 second to 1 hour, preferably about 5 seconds to 30 minutes, and more preferably about 5 seconds to 10 minutes. The coating film may be allowed to stand (natural drying) before and after drying or heat treatment of the coating film. It is preferable to form a cured product of the coating film by irradiating the coating film formed from the dispersion with electromagnetic radiation (particularly, ultraviolet rays).
　塗膜に電磁波を照射する場合、そのための光源としては、例えば、メタルハライドランプ、高圧水銀灯、超高圧水銀灯、低圧水銀灯、キセノンランプ、アークランプ、レーザーなどが挙げられる。これらの中で、メタルハライドランプ、高圧水銀灯、超高圧水銀灯、低圧水銀灯が好ましい。電磁線照射のピーク照度は、好ましくは５～２０００ｍＷ／ｃｍ２であり、より好ましくは１０～２０００ｍＷ／ｃｍ２である。積算照射量は、好ましくは２０～３０００ｍＪ／ｃｍ２であり、より好ましくは１００～２５００ｍＪ／ｃｍ２である。 In the case of irradiating the coating film with electromagnetic waves, examples of the light source therefor include a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, an arc lamp, and a laser. Among these, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a low pressure mercury lamp are preferable. The peak illuminance of electromagnetic radiation is preferably 5 to 2000 mW / cm 2 , more preferably 10 to 2000 mW / cm 2 . Integrated irradiation dose is preferably 20 ~ 3000mJ / cm 2, more preferably 100 ~ 2500mJ / cm 2.
　分散液を被着体に塗布する前に、第１の基材に表面処理を施してもよい。表面処理としては、例えば、プライマー処理、ブラスト処理、薬品処理、脱脂処理、火炎処理、酸化処理、蒸気処理、コロナ放電処理、紫外線照射処理、プラズマ処理、イオン処理およびアンカー層の形成等が挙げられる。 Before the dispersion is applied to the adherend, a surface treatment may be applied to the first substrate. Examples of the surface treatment include primer treatment, blast treatment, chemical treatment, degreasing treatment, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and anchor layer formation. .
　乾燥後の塗膜では、分散液に含有されていた水の９５重量％以上が除去されていることが好ましい。このように塗膜中の水分を低減することにより、塗膜およびそれから得られる硬化物の接着性を確保することができる。 It is preferable that 95% by weight or more of the water contained in the dispersion is removed from the dried coating film. Thus, the adhesiveness of a coating film and the hardened | cured material obtained from it can be ensured by reducing the water | moisture content in a coating film.
　乾燥後の塗膜の厚さは、好ましくは０．０１～３００μｍ程度、より好ましくは０．０１～２００μｍ程度、さらに好ましくは０．０１～５０μｍ程度である。 The thickness of the coated film after drying is preferably about 0.01 to 300 μm, more preferably about 0.01 to 200 μm, and still more preferably about 0.01 to 50 μm.
　次いで、分散液を塗布した第１の基材および第２の基材の少なくとも一方に液状の接着剤を塗布し、乾燥または加熱処理する。これら塗布および乾燥または加熱処理は、第１の基材および第２の基材の少なくとも一方にのみ１回行なえばよいが、双方に、１回以上の接着剤の塗布および加熱乾燥を行なってもよい。接着剤の塗布方法、乾燥後の塗膜の厚さ、乾燥または加熱処理の方法、温度および時間等の条件等は、適宜変更することができる。上述した分散液の塗布等と同じ条件を選択してもよいし、異なる条件を選択してもよい。 Next, a liquid adhesive is applied to at least one of the first substrate and the second substrate to which the dispersion is applied, and is dried or heat-treated. These application and drying or heat treatment may be performed only once on at least one of the first base material and the second base material, but both the application and heat drying of the adhesive may be performed on both of them. Good. The application method of the adhesive, the thickness of the coating film after drying, the method of drying or heat treatment, conditions such as temperature and time, etc. can be changed as appropriate. The same conditions as the dispersion application described above may be selected, or different conditions may be selected.
　第１の基材および第２の基材の双方に接着剤を塗布する場合、第１の基材および第２の基材に対して同じ接着剤を塗布してもよく、異なる接着剤を塗布してもよい。第１の基材および第２の基材を良好に接着させるためには、同じ接着剤を用いることが好ましい。接着剤は、上で用いた分散液であってもよいし、市販の接着剤であってもよい。 When applying an adhesive to both the first substrate and the second substrate, the same adhesive may be applied to the first substrate and the second substrate, or different adhesives may be applied. May be. In order to adhere the first substrate and the second substrate satisfactorily, it is preferable to use the same adhesive. The adhesive may be the dispersion used above or a commercially available adhesive.
　接着剤層の厚さは、用いる接着剤の組成、基材の材料および形態等によって適宜調整することができる。接着剤層の厚さは、好ましくは０．０１～３００μｍ程度、より好ましくは０．０１～２００μｍ程度である。 The thickness of the adhesive layer can be appropriately adjusted depending on the composition of the adhesive used, the material and form of the substrate, and the like. The thickness of the adhesive layer is preferably about 0.01 to 300 μm, more preferably about 0.01 to 200 μm.
　液状の接着剤を被着体（第１の基材および／または第２の基材）に塗布する前に、被着体に上述の表面処理を施してもよい。 Prior to applying the liquid adhesive to the adherend (first substrate and / or second substrate), the adherend may be subjected to the surface treatment described above.
　分散液および／または接着剤が塗布された、第１の基材および第２の基材を貼り合せる方法としては、特に限定はなく、これらを機械的操作または手動で貼り合せればよい。貼り合せの際、熱、圧力またはその双方を加えてもよい。加熱する場合には、第１の基材および第２の基材並びに接着剤層が変質しない温度範囲で加熱とすることが必要であり、加熱温度は、好ましくは１２０℃程度以下、より好ましくは１００℃程度以下である。加熱は、通常の熱風循環型のオーブン、赤外線ヒーター、電子レンジ等を用いて行なうことができる。加圧する場合、その圧力は、例えば１００ｇ／ｃｍ２程度以上、且つ第１の基材および第２の基材の形状が変形する圧力未満である。加熱および／または加圧する場合、その時間は、例えば、１秒～１０日間程度である。 The method for bonding the first substrate and the second substrate to which the dispersion and / or the adhesive is applied is not particularly limited, and these may be bonded by mechanical operation or manually. During bonding, heat, pressure, or both may be applied. In the case of heating, it is necessary to set the heating within a temperature range in which the first base material, the second base material, and the adhesive layer do not deteriorate, and the heating temperature is preferably about 120 ° C. or less, more preferably It is about 100 ° C. or lower. Heating can be performed using a normal hot air circulating oven, an infrared heater, a microwave oven, or the like. When pressurizing, the pressure is, for example, about 100 g / cm 2 or more and less than the pressure at which the shapes of the first base material and the second base material are deformed. When heating and / or pressurizing, the time is, for example, about 1 second to 10 days.
　第１の基材および第２の基材としては、例えば、上述した被着体と同様のものが挙げられる。第１の基材は、好ましくはオレフィン系重合体またはエチレン－酢酸ビニル共重合体からなる基材である。第２の基材は、好ましくは、ポリ塩化ビニル、合成皮革、ゴム、綿含有繊維およびポリオレフィン系重合体からなる群から選ばれる基材である。 Examples of the first base material and the second base material include those similar to the adherend described above. The first substrate is preferably a substrate made of an olefin polymer or an ethylene-vinyl acetate copolymer. The second base material is preferably a base material selected from the group consisting of polyvinyl chloride, synthetic leather, rubber, cotton-containing fibers, and polyolefin polymers.
　接着剤層は、例えば、液状のポリウレタン接着剤、液状のゴム系接着剤、液状のアクリル接着剤、または液状のエポキシ接着剤等を塗布し、水や有機溶剤などを除去することにより得られる。 The adhesive layer can be obtained, for example, by applying a liquid polyurethane adhesive, a liquid rubber adhesive, a liquid acrylic adhesive, or a liquid epoxy adhesive, and removing water, an organic solvent, or the like.
　液状のポリウレタン接着剤としては、例えば、上述した水溶性または水分散性ポリウレタン等が挙げられる。
　液状のゴム系接着剤としては、例えば、天然ゴム、クロロプレンゴム、スチレン－ブタジエン共重合ゴム（ＳＢＲ）、イソブチレンゴム、ブチルゴム、スチレン－イソプレン－スチレンブロック共重合ゴム（ＳＩＳ）、スチレン－ブタジエン－スチレンブロック共重合ゴム（ＳＢＳ）、ブタジエン－アクリロニトリル共重合ゴム（ＮＢＲ）、ブタジエンゴム（ＢＲ）等のゴム成分を含む液状の接着剤が挙げられる。ゴム成分は、１種のみを使用してもよく、２種以上を併用してもよい。また、これらゴム成分に加えて、ロジン樹脂、テルペン樹脂、石油樹脂等の接着付与樹脂をゴム系接着剤に添加してもよい。 Examples of the liquid polyurethane adhesive include the above-described water-soluble or water-dispersible polyurethane.
Examples of liquid rubber adhesives include natural rubber, chloroprene rubber, styrene-butadiene copolymer rubber (SBR), isobutylene rubber, butyl rubber, styrene-isoprene-styrene block copolymer rubber (SIS), and styrene-butadiene-styrene. Examples thereof include liquid adhesives containing rubber components such as block copolymer rubber (SBS), butadiene-acrylonitrile copolymer rubber (NBR), and butadiene rubber (BR). Only 1 type may be used for a rubber component and it may use 2 or more types together. In addition to these rubber components, an adhesion-imparting resin such as rosin resin, terpene resin, and petroleum resin may be added to the rubber adhesive.
　液状のアクリル接着剤としては、例えば、粘着成分としてアクリル酸エステルおよび／またはメタクリル酸エステルと、官能基含有モノマーと、凝集力を向上させることを目的としたモノマーとの共重合体を含む液状の接着剤が挙げられる。液状のアクリル系接着剤には、イソシアネート架橋剤、キレート架橋剤、エポキシ架橋剤等を添加してもよい。 Examples of the liquid acrylic adhesive include a liquid containing a copolymer of an acrylic ester and / or methacrylic ester as an adhesive component, a functional group-containing monomer, and a monomer intended to improve cohesion. An adhesive is mentioned. An isocyanate crosslinking agent, a chelate crosslinking agent, an epoxy crosslinking agent, or the like may be added to the liquid acrylic adhesive.
　アクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸ｎ－アミル、アクリル酸イソアミル、アクリル酸ｎ－ヘキシル、アクリル酸２－エチルヘキシル、アクリル酸ｎ－オクチル、アクリル酸ｎ－ラウリル等を好ましく例示することができる。メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸イソプロピル、メタクリル酸ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸ｎ－アミル、メタクリル酸イソアミル、メタクリル酸ｎ－ヘキシル、メタクリル酸２－エチルヘキシル、メタクリル酸ｎ－オクチル、メタクリル酸ｎ－ラウリル等を好ましく例示することができる。 Examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, Preferred examples include n-octyl acrylate and n-lauryl acrylate. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Preferred examples include n-octyl methacrylate and n-lauryl methacrylate.
　アクリル酸エステルおよび／またはメタクリル酸エステルと共重合可能な官能基含有モノマーとしては、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等のα，β－不飽和カルボン酸；アクリル酸ヒドロキシエチル、アクリル酸ヒドロキシブロピル、メタクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシプロピル等のアクリル酸またはメタクリル酸のヒドロキシアルキルエステル；アクリルアミド、メタクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－ブトキシメタクリルアミド等のＮ－置換または未置換アクリルアミド；メタクリル酸グリシジル、メタクリル酸グリシジル等のアクリル酸またはメタクリル酸のグリシジルエステル；アクリロニトリル等を好ましく例示することができる。 Examples of the functional group-containing monomer copolymerizable with acrylic acid ester and / or methacrylic acid ester include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; acrylic Hydroxyethyl ester, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. acrylic acid or hydroxyalkyl ester of methacrylic acid; acrylamide, methacrylamide, diacetone (meth) acrylamide, N-methylolacrylamide, N-methylol N-substituted or unsubstituted acrylamide such as methacrylamide, N-butoxymethylacrylamide, N-butoxymethacrylamide; acrylic acid such as glycidyl methacrylate and glycidyl methacrylate Or, preferred examples include glycidyl ester of methacrylic acid; acrylonitrile and the like.
　液状のエポキシ接着剤としては、例えば、平均して１分子当たり１以上のエポキシ基を有するエポキシ樹脂を含む液状の接着剤が挙げられる。エポキシ樹脂としては、ビスフェノールＡとエピクロルヒドリンから得られるエポキシ樹脂、ビスフェノールＦとエピクロルヒドリンまたは水素化ビスフェノールＡとエピクロルヒドリンから得られるポリグリシジルエーテル等が例示される。この他、オキサゾリドン変性エポキシ樹脂、ノボラック型エポキシ樹脂、多官能フェノール型エポキシ樹脂、各種のハロゲン化エポキシ樹脂、グリシジルエステル型エポキシ樹脂、ポリグリコール型エポキシ樹脂、環状脂肪族エポキシ樹脂等も用いることができる。これらのエポキシ樹脂は、単独で使用してもよく、２種以上を併用してもよい。 Examples of the liquid epoxy adhesive include a liquid adhesive containing an epoxy resin having one or more epoxy groups per molecule on average. Examples of the epoxy resin include an epoxy resin obtained from bisphenol A and epichlorohydrin, a polyglycidyl ether obtained from bisphenol F and epichlorohydrin, or hydrogenated bisphenol A and epichlorohydrin. In addition, oxazolidone-modified epoxy resins, novolac type epoxy resins, polyfunctional phenol type epoxy resins, various halogenated epoxy resins, glycidyl ester type epoxy resins, polyglycol type epoxy resins, cycloaliphatic epoxy resins, and the like can also be used. . These epoxy resins may be used alone or in combination of two or more.
　液状のポリウレタン接着剤、液状のゴム系接着剤、液状のアクリル接着剤および液状のエポキシ接着剤は、溶液、分散液または乳濁液の形態の接着剤でもよく、溶融状態で用いられるホットメルト接着剤でもよい。 Liquid polyurethane adhesives, liquid rubber adhesives, liquid acrylic adhesives and liquid epoxy adhesives may be in the form of solutions, dispersions or emulsions, and hot melt adhesives used in the molten state An agent may be used.
　接着剤層を構成する接着剤は、上述した成分とは異なる他の成分（例えば、樹脂）を含有していてもよい。接着剤が含有していてもよい樹脂としては、例えば、オレフィン系樹脂、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニリデン、ポリスチレン（ＰＳ）、ポリ酢酸ビニル（ＰＶＡｃ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、ＡＳ樹脂、前記樹脂の変性物等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 The adhesive constituting the adhesive layer may contain another component (for example, resin) different from the above-described components. Examples of the resin that the adhesive may contain include, for example, an olefin resin, polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polytetrafluoroethylene (PTFE), Examples include acrylonitrile-butadiene-styrene copolymer (ABS resin), AS resin, and modified products of the resin. These may be used alone or in combination of two or more.
　また、接着剤が含有していてもよい樹脂としては、例えば、粘着付与樹脂が挙げられる。粘着付与樹脂としては、例えば、ロジン類、テルペン系樹脂、炭素数５の石油留分を重合した石油系樹脂およびこの水素添加樹脂、炭素数９の石油留分を重合した石油系樹脂およびこの水素添加樹脂、その他の石油系樹脂、クマロン樹脂並びにインデン樹脂、ポリウレタン樹脂等が挙げられる。 Also, examples of the resin that the adhesive may contain include a tackifier resin. Examples of tackifying resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogens thereof. Examples thereof include additive resins, other petroleum-based resins, coumarone resins, indene resins, polyurethane resins, and the like.
　また、接着剤が含有していてもよい他の成分としては、例えば、界面活性剤、光重合開始剤、光安定剤、紫外線硬化性オリゴマー、蛍光増白剤、レベリング剤、塩基性化合物、有機溶剤、架橋剤、光増感剤、フェノール系安定剤、フォスファイト系安定剤、アミン系安定剤、アミド系安定剤、老化防止剤、耐候安定剤、沈降防止剤、酸化防止剤、熱安定剤、揺変剤、増粘剤、消泡剤、粘度調整剤、耐候剤、顔料分散剤、帯電防止剤、滑剤、核剤、難燃剤、油剤、染料、硬化剤；酸化チタン（ルチル型）および酸化亜鉛などの遷移金属化合物；カーボンブラック等の顔料；ガラス繊維、炭素繊維、チタン酸カリウム繊維、ウオラストナイト、炭酸カルシウム、硫酸カルシウム、タルク、ガラスフレーク、硫酸バリウム、クレー、カオリン、微粉末シリカ、マイカ、珪酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、酸化アルミニウム、酸化マグネシウム、およびセライトなどの無機または有機の充填剤；等が挙げられる。 Examples of other components that the adhesive may contain include, for example, surfactants, photopolymerization initiators, light stabilizers, ultraviolet curable oligomers, fluorescent brighteners, leveling agents, basic compounds, and organic compounds. Solvents, crosslinking agents, photosensitizers, phenolic stabilizers, phosphite stabilizers, amine stabilizers, amide stabilizers, anti-aging agents, weathering stabilizers, antisettling agents, antioxidants, thermal stabilizers , Thixotropic agents, thickeners, antifoaming agents, viscosity modifiers, weathering agents, pigment dispersants, antistatic agents, lubricants, nucleating agents, flame retardants, oil agents, dyes, curing agents; titanium oxide (rutile type) and Transition metal compounds such as zinc oxide; pigments such as carbon black; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, kaolin, fine End silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, and fillers of inorganic or organic, such as Celite, and the like.
　以下に、実施例等を挙げて本発明を詳細に説明するが、本発明は以下の実施例等によって制限を受けるものではなく、上記・下記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。
　なお、以下に記載の「部」、「％」および「ｐｐｍ」は、特に断らない限り、それぞれ「重量部」、「重量％」および「重量ｐｐｍ」を意味する。 Hereinafter, the present invention will be described in detail with reference to examples and the like, but the present invention is not limited by the following examples and the like, and appropriate modifications are made within a range that can meet the above and the following purposes. Of course, it is also possible to implement them, and they are all included in the technical scope of the present invention.
In the following, “parts”, “%” and “ppm” mean “parts by weight”, “wt%” and “wt ppm” unless otherwise specified.
　塩素化ゴムの塩素原子含有量は、フラスコ燃焼－イオンクロマトグラフ法により測定した値である。
　下記表に記載の分散質のメジアン径（体積基準）は、ＨＯＲＩＢＡ製作所製、レーザー回折粒子径測定装置ＬＡ－９５０Ｖ２で測定した値である。 The chlorine atom content of the chlorinated rubber is a value measured by a flask combustion-ion chromatography method.
The median diameter (volume basis) of the dispersoids described in the following table is a value measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA Corporation.
　後方散乱光強度の測定試料を調製するための自転公転撹拌機として、シンキー社製「自転・公転ミキサー　あわとり練太郎　ＡＲＥ－３１０」を使用した。
　測定試料の後方散乱光強度を測定する装置として、Ｆｏｒｍｕｌａｔｉｏｎ社製「タービスキャンＴＯＷＥＲ」を使用した。
　前記自転公転撹拌機を使用して、後述の実施例および比較例で製造した分散液から測定試料を調製し、試料調製から１０分以内に測定を開始し、試料セル中の測定試料の上部、中間部および底部のそれぞれにおける、測定を開始してから３０分後に測定した後方散乱光強度（％）に対する、測定を開始してから２４時間後に測定した後方散乱光強度（％）の変化量の絶対値における最大値αを算出し、以下の基準で評価した。結果を下記表に示す。
○：上記式（I）～(III)の要件を全て満たす。
×：上記式（I）～(III)の要件のいずれかまたは全てを満たさない。 As a rotating and rotating stirrer for preparing a measurement sample of the backscattered light intensity, “Rotating and Revolving Mixer Awatori Nertaro ARE-310” manufactured by Shinky Corporation was used.
As a device for measuring the backscattered light intensity of the measurement sample, “Turbiscan TOWER” manufactured by Formulation was used.
Using the rotation and revolution stirrer, a measurement sample is prepared from the dispersions produced in Examples and Comparative Examples described later, and the measurement is started within 10 minutes from the sample preparation, and the upper part of the measurement sample in the sample cell; The amount of change in backscattered light intensity (%) measured 24 hours after the start of measurement, relative to the backscattered light intensity (%) measured 30 minutes after the start of measurement at each of the intermediate part and the bottom part The maximum value α in absolute value was calculated and evaluated according to the following criteria. The results are shown in the table below.
○: All the requirements of the above formulas (I) to (III) are satisfied.
×: Does not satisfy any or all of the requirements of the above formulas (I) to (III).
　実施例および比較例で使用した塩素化ゴム、重合性基を有する化合物、光重合開始剤、界面活性剤、およびレベリング剤は以下の通りである。
　塩素化ゴム１：ペルグートＳ２０（コベストロ社、塩素原子含有量：６４．５％以上、融点：２５０℃、ポリスチレン換算の重量平均分子量（Ｍｗ）：７５，０００、カルボキシ基およびカルボン酸無水物構造を有さない塩素化ゴム）
　重合性基を有する化合物１：ドデシルメタクリレート（９７０ｐｐｍの４－メトキシフェノールを含有、東京化成工業社）
　重合性基を有する化合物２：１，６－ヘキサンジオール　ジメタクリレート（６０ｐｐｍの４－メトキシフェノールを含有、東京化成工業社）
　重合性基を有する化合物３：２－フェノキシエチレングリコール　メタクリレート（１００ｐｐｍの４－メトキシフェノールを含有、新中村化学社）
　重合性基を有する化合物４：トリシクロデカンジメタノール　ジアクリレート（８００ｐｐｍの４－メトキシフェノールを含有、新中村化学社）
　重合性基を有する化合物５：トリシクロデカンジメタノール　ジメタクリレート（３００ｐｐｍの４－メトキシフェノール含有、新中村化学社）
　光重合開始剤１：２－ヒドロキシ－２－メチルプロピオフェノン（東京化成工業社）
　界面活性剤１：アクアロン　ＫＨ－1０（第一工業製薬（株））
　界面活性剤２：エマルゲン１０９Ｐ（花王（株））
　塩基性化合物１：２－（ジメチルアミノ）エタノール（東京化成工業社）
　蛍光増白剤１：Ｎｉｋｋａｆｌｕｏｒ　ＯＢ（（株）日本化学工業所）
　レベリング剤１：ＢＹＫ－３４９（ビックケミー・ジャパン社） The chlorinated rubber, the compound having a polymerizable group, the photopolymerization initiator, the surfactant, and the leveling agent used in Examples and Comparative Examples are as follows.
Chlorinated rubber 1: Pergut S20 (Covestro, chlorine atom content: 64.5% or more, melting point: 250 ° C., weight average molecular weight (Mw) in terms of polystyrene: 75,000, carboxy group and carboxylic anhydride structure Chlorinated rubber that does not have)
Compound 1 having polymerizable group: dodecyl methacrylate (containing 970 ppm 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound having a polymerizable group 2: 1,6-hexanediol dimethacrylate (containing 60 ppm of 4-methoxyphenol, Tokyo Chemical Industry Co., Ltd.)
Compound having polymerizable group 3: 2-phenoxyethylene glycol methacrylate (containing 100 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Compound 4 having a polymerizable group: tricyclodecane dimethanol diacrylate (containing 800 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Compound 5 having a polymerizable group: tricyclodecane dimethanol dimethacrylate (containing 300 ppm of 4-methoxyphenol, Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 1: 2-hydroxy-2-methylpropiophenone (Tokyo Chemical Industry Co., Ltd.)
Surfactant 1: Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 2: Emulgen 109P (Kao Corporation)
Basic compound 1: 2- (dimethylamino) ethanol (Tokyo Chemical Industry Co., Ltd.)
Fluorescent whitening agent 1: Nikkafluor OB (Nippon Chemical Industry Co., Ltd.)
Leveling agent 1: BYK-349 (Big Chemie Japan)
＜製造例１：分散液Ｅ１の製造＞
　攪拌機、温度計、および還流冷却管を備えたセパラブルフラスコ反応容器に、塩素化ゴム１（１５部）、重合性基を有する化合物１（３０部）、重合性基を有する化合物２（４５部）、および重合性基を有する化合物３（１０部）、光重合開始剤１（１部）を仕込み、６０℃にて攪拌して、溶液（以下「溶液１」と記載する）を調製し、溶液１を室温に冷却した。 <Production Example 1: Production of Dispersion E1>
In a separable flask reaction vessel equipped with a stirrer, thermometer, and reflux condenser, chlorinated rubber 1 (15 parts), compound 1 having a polymerizable group (30 parts), compound 2 having a polymerizable group (45 parts) ), And a compound 3 (10 parts) having a polymerizable group and a photopolymerization initiator 1 (1 part), and stirred at 60 ° C. to prepare a solution (hereinafter referred to as “solution 1”). Solution 1 was cooled to room temperature.
　界面活性剤１（５部）をイオン交換水（３００部）に入れ、６０℃で撹拌して、界面活性剤１の水溶液（以下「溶液２」と記載する）を調製した。 Surfactant 1 (5 parts) was placed in ion-exchanged water (300 parts) and stirred at 60 ° C. to prepare an aqueous solution of surfactant 1 (hereinafter referred to as “solution 2”).
　室温にて、溶液１に、溶液２を添加し、撹拌して、混合物を調製した。次いで、室温にて、ホモミキサーＭＡＲＫＩＩを取り付けたＴＫロボミクス（（株）ＰＲＩＭＩＸ製）を用いて、得られた混合物を１６，０００ｒｐｍで５分間攪拌して、乳白色の乳濁液を得た。分散液を室温まで冷却してから、８００ｂａｒで（株）エスエムテー製の高圧ホモジナイザー「ＬＡＢ１０００」を用いて、均質化処理を４回行い、得られた乳濁液を２００メッシュナイロン網にて濾過し、乳濁液である分散液Ｅ１を得た。得られた分散液Ｅ１の不揮発分濃度は２５％であった。 At room temperature, solution 2 was added to solution 1 and stirred to prepare a mixture. Subsequently, the obtained mixture was stirred at 16,000 rpm for 5 minutes at room temperature using TK Robotics (manufactured by PRIMIX Co., Ltd.) equipped with a homomixer MARKII to obtain a milky white emulsion. After cooling the dispersion to room temperature, homogenization was performed 4 times using a high-pressure homogenizer “LAB1000” manufactured by SMT Co., Ltd. at 800 bar, and the resulting emulsion was filtered through a 200 mesh nylon net. A dispersion E1 which is an emulsion was obtained. The obtained dispersion E1 had a nonvolatile content concentration of 25%.
＜製造例２～７：分散液Ｅ２～Ｅ７の製造＞
　表１に示す量の塩素化ゴム、重合性基を有する化合物、光重合開始剤、界面活性剤、およびイオン交換水を使用したこと以外は製造例１と同様にして、乳濁液である分散液Ｅ２～Ｅ７を得た。なお、製造例６では、表１に示す量の蛍光増白剤を添加した溶液を使用して分散液Ｅ６を製造した。製造例７では、光重合開始剤を使用せずに、分散液Ｅ７を製造した。 <Production Examples 2 to 7: Production of dispersions E2 to E7>
Dispersion as an emulsion in the same manner as in Production Example 1 except that chlorinated rubber, a compound having a polymerizable group, a photopolymerization initiator, a surfactant, and ion-exchanged water in the amounts shown in Table 1 were used. Liquids E2 to E7 were obtained. In Production Example 6, Dispersion E6 was produced using a solution to which the amount of fluorescent whitening agent shown in Table 1 was added. In Production Example 7, Dispersion E7 was produced without using a photopolymerization initiator.
＜製造例８～１２：分散液Ｅ８～Ｅ１２の製造＞
　表１に示す塩素化ゴム、重合性基を有する化合物、光重合開始剤、界面活性剤、およびイオン交換水の量、ホモミキサーによる撹拌時間、高圧ホモジナイザーによる均質化処理の回数以外は製造例１と同様にして、乳濁液である分散液Ｅ８～Ｅ１２を得た。なお、製造例１２では、表１に示す量の塩基性化合物を添加した溶液を使用して分散液Ｅ１２を製造した。 <Production Examples 8 to 12: Production of dispersions E8 to E12>
Production Example 1 except for the amount of chlorinated rubber, a compound having a polymerizable group, a photopolymerization initiator, a surfactant, and ion-exchanged water shown in Table 1, the stirring time by a homomixer, and the number of times of homogenization by a high-pressure homogenizer In the same manner, dispersions E8 to E12 as emulsions were obtained. In Production Example 12, dispersion E12 was produced using a solution to which the basic compound in the amount shown in Table 1 was added.
　製造例１～１２で製造した分散液の種類；使用した成分の種類および量（部）；得られた分散液中の塩素化ゴムおよび重合性基を有する化合物の合計量（％）、塩素化ゴムの量（％）、重合性基を有し、且つ環状構造を有さない化合物の量（％）、並びに重合性基および環状構造を有する化合物の量（％）（全て、塩素化ゴム、重合性基を有する化合物および水の合計に対する値である）；ホモミキサーによる撹拌時間（分）；高圧ホモジナイザーによる処理回数；並びに分散質のメジアン径（μｍ）の評価結果を、下記表１に示す。 Types of dispersions produced in Production Examples 1 to 12; types and amounts of components used (parts); total amount (%) of chlorinated rubber and compounds having a polymerizable group in the obtained dispersions, chlorination Amount of rubber (%), amount of compound having a polymerizable group and having no cyclic structure (%), and amount of compound having a polymerizable group and a cyclic structure (%) (all chlorinated rubber, Table 1 shows the evaluation results of the stirring time (minutes) by the homomixer; the number of treatments by the high-pressure homogenizer; and the median diameter (μm) of the dispersoid. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜実施例１～７および比較例１～５：水系接着剤Ｆ１～Ｆ１２の製造＞
　表２に示す量の、分散液Ｅ１～Ｅ１２のいずれか、レベリング剤１（ＢＹＫ（登録商標）－３４９、ビックケミー・ジャパン社）、およびイオン交換水を混合し、スリーワンモーターで攪拌して、乳濁液である水系接着剤Ｆ１～Ｆ１２を得た。
　なお、実施例１～７および比較例１～５以降では、レベリング剤をさらに含有し、接着剤として好適な分散液を「水系接着剤」と記載する。 <Examples 1 to 7 and Comparative Examples 1 to 5: Production of aqueous adhesives F1 to F12>
Any one of dispersions E1 to E12, leveling agent 1 (BYK (registered trademark) -349, Big Chemie Japan), and ion-exchanged water in the amounts shown in Table 2 are mixed, stirred with a three-one motor, and mixed with milk. Water-based adhesives F1 to F12 as turbid liquids were obtained.
In Examples 1 to 7 and Comparative Examples 1 to 5 and later, a dispersion that further contains a leveling agent and is suitable as an adhesive is referred to as an “aqueous adhesive”.
　実施例１～７および比較例１～５で製造した水系接着剤の種類；使用した分散液の種類および量（部）；使用したレベリング剤１およびイオン交換水の量（部）；得られた水系接着剤中の塩素化ゴムおよび重合性基を有する化合物の合計量（％）、塩素化ゴムの量（％）、重合性基を有し、且つ環状構造を有さない化合物の量（％）、並びに重合性基および環状構造を有する化合物の量（％）（全て、塩素化ゴム、重合性基を有する化合物および水の合計に対する値である）；分散質のメジアン径（μｍ）；並びに後方散乱光強度の変化量の評価結果を、下記表２に示す。 Types of water-based adhesives produced in Examples 1 to 7 and Comparative Examples 1 to 5; types and amounts (parts) of used dispersions; amounts of leveling agent 1 and ion-exchanged water (parts) used; obtained Total amount (%) of chlorinated rubber and compound having polymerizable group in aqueous adhesive, amount of chlorinated rubber (%), amount of compound having polymerizable group and having no cyclic structure (%) ), And the amount of the compound having a polymerizable group and a cyclic structure (%) (all values are based on the sum of chlorinated rubber, the compound having a polymerizable group and water); the median diameter of the dispersoid (μm); and The evaluation results of the amount of change in the backscattered light intensity are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
＜製造例１３：液状の接着剤１の製造＞
　ポリウレタンエマルション（ディスパコール（登録商標）Ｕ－５４、住化コベストロウレタン（株））、イソシアナート（デスモジュール（登録商標）Ｎ３３００、住化コベストロウレタン（株））、およびレベリング剤１を、ポリウレタンエマルション：イソシアナート：レベリング剤１の不揮発分の比が１００部：５部：１部となるように混合して、乳濁液である接着剤１を得た。 <Production Example 13: Production of liquid adhesive 1>
Polyurethane emulsion (Dispacol (registered trademark) U-54, Sumika Cobestrourethane Co., Ltd.), isocyanate (Desmodur (registered trademark) N3300, Sumika Covestrourethane Co., Ltd.), and leveling agent 1, Adhesive 1 which was an emulsion was obtained by mixing the polyurethane emulsion: isocyanate: leveling agent 1 so that the nonvolatile content ratio was 100 parts: 5 parts: 1 part.
＜実施例８：積層体１の製造＞
　水系接着剤Ｆ１を、送風定温恒温器にて５０℃で７日間放置した後に、はけを用いて、第１の基材であるエチレン－酢酸ビニル共重合体（ＥＶＡ）の発泡体に塗布（乾燥後の塗膜の単位面積あたりの重量：約３ｇ／ｍ２）し、７０℃で５分間乾燥し、コンベア式ＵＶ照射装置（アイグラフィックス株式会社製、アイグランデージＥＣＳ－４０１１ＧＸ）で紫外線を照射して、ＥＶＡと硬化物との積層体を得た（ランプ：高圧水銀ランプ、ランプ出力：３ｋＷ、ランプ高さ：１１０ｍｍ、コンベアスピード：２７６ｍ／ｍｉｎ、ピーク照度：２５０ｍＷ／ｃｍ２、積算照射量：７００ｍＪ／ｃｍ２（紫外線積算光量計ＵＶＩＣＵＲＥ　ＰＬＵＳ　ＩＩ、ＵＶ－Ａ測定値、ＦｕｓｉｏｎＵＶ　Ｓｙｓｔｅｍｓ　Ｊａｐａｎ　Ｋ．Ｋ．）。 <Example 8: Production of laminate 1>
The water-based adhesive F1 was allowed to stand at 50 ° C. for 7 days in a blowing constant temperature incubator, and then applied to a foam of ethylene-vinyl acetate copolymer (EVA) as a first substrate using a brush ( Weight per unit area of the coated film after drying: about 3 g / m 2 ), dried at 70 ° C. for 5 minutes, and irradiated with ultraviolet rays using a conveyor type UV irradiation device (Eye Graphics Co., Ltd., Eye Grandage ECS-4011GX). Irradiated to obtain a laminate of EVA and cured product (lamp: high pressure mercury lamp, lamp output: 3 kW, lamp height: 110 mm, conveyor speed: 276 m / min, peak illuminance: 250 mW / cm 2 , integrated irradiation Amount: 700 mJ / cm 2 (UV integrated light meter UVICURE PLUS II, UV-A measured value, FusionUV Systems Japan KK).
　続いて、第２の基材である綿帆布（城北工業社）に接着剤１を、はけを用いて塗布し（乾燥後の塗膜の単位面積あたりの重量：約５０ｇ／ｍ２）、７０℃で５分間オーブン乾燥し、綿帆布と接着剤層との積層体を得た。 Subsequently, the adhesive 1 was applied to a cotton canvas (Johoku Kogyo Co., Ltd.) as the second substrate using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), It was oven dried at 70 ° C. for 5 minutes to obtain a laminate of cotton canvas and adhesive layer.
　上記のようにして得られたＥＶＡと硬化物との積層体の硬化物側の表面、および綿帆布と接着剤層との積層体の接着剤層側の表面に、それぞれ接着剤１を、はけを用いて塗布し（乾燥後の塗膜の単位面積あたりの重量：約５０ｇ／ｍ２）、７０℃で５分間オーブン乾燥した。その後、得られたＥＶＡと硬化物と接着剤層との積層体および綿帆布と接着剤層との積層体の、接着剤層同士を貼り合せ、手で圧着し、さらにプレスにて３ＭＰａで２０秒間圧着して、ＥＶＡ（第１の基材）と硬化物と接着剤層と綿帆布（第２の基材）との積層体である積層体１を得た。 Adhesive 1 is applied to the surface on the cured product side of the laminate of EVA and cured product obtained as described above, and the surface on the adhesive layer side of the laminate of cotton canvas and adhesive layer, respectively. The film was applied using a brush (weight per unit area of the coated film after drying: about 50 g / m 2 ), and oven-dried at 70 ° C. for 5 minutes. Thereafter, the adhesive layers of the obtained EVA, cured product and adhesive layer laminate and cotton canvas and adhesive layer laminate were bonded together, pressure-bonded by hand, and further pressed at 3 MPa at 20 MPa. The laminated body 1 which is a laminated body of EVA (1st base material), hardened | cured material, an adhesive bond layer, and cotton canvas (2nd base material) was obtained by crimping for 2 seconds.
＜実施例９～１４および比較例６～１０：積層体２～１２の製造＞
　水系接着剤Ｆ１を、水系接着剤Ｆ２～Ｆ１２のいずれかに変更したこと以外は実施例８と同様にして、ＥＶＡ（第１の基材）と硬化物と接着剤層と綿帆布（第２の基材）との積層体である積層体２～１２を得た。 <Examples 9 to 14 and Comparative Examples 6 to 10: Production of Laminates 2 to 12>
EVA (first substrate), cured product, adhesive layer, cotton canvas (second), except that the water-based adhesive F1 was changed to any one of the water-based adhesives F2 to F12. Laminated bodies 2 to 12 which are laminated bodies with the base material) were obtained.
　なお、上記実施例８～１４および比較例６～１０では、実施例１～７および比較例１～５で得られた水系接着剤Ｆ１～Ｆ１２の長期保存後の接着性を評価するために、上述したように、５０℃で７日間保存した水系接着剤Ｆ１～Ｆ１２を用いて、積層体１～１２を製造した。なお、５０℃で７日間保存した水系接着剤の接着性は、室温で数ヶ月保存した水系接着剤の接着性に対応すると考えることができる。 In Examples 8 to 14 and Comparative Examples 6 to 10, in order to evaluate the adhesiveness of the aqueous adhesives F1 to F12 obtained in Examples 1 to 7 and Comparative Examples 1 to 5 after long-term storage, As described above, laminates 1 to 12 were produced using aqueous adhesives F1 to F12 stored at 50 ° C. for 7 days. In addition, it can be considered that the adhesiveness of the aqueous adhesive stored for 7 days at 50 ° C. corresponds to the adhesiveness of the aqueous adhesive stored for several months at room temperature.
＜試験例１：初期接着性の評価＞
　積層体を、その製造後に室温で５分間放置してから、剥離速度５０ｍｍ／分、剥離角度１８０度および室温の条件下で引張り試験機（島津製作所社製、オートグラフ）を用いて、積層体におけるＥＶＡ（第１の基材）と綿帆布（第２の基材）との剥離強度を測定し、以下の基準で初期接着性を評価した。結果を表３に示す。
　○：剥離強度が４５Ｎ／ｉｎｃｈ以上
　×：剥離強度が４５Ｎ／ｉｎｃｈ未満 <Test Example 1: Evaluation of initial adhesiveness>
The laminate is allowed to stand at room temperature for 5 minutes after the production, and is then laminated using a tensile tester (manufactured by Shimadzu Corp., Autograph) under the conditions of a peeling rate of 50 mm / min, a peeling angle of 180 degrees, and room temperature. The peel strength between EVA (first substrate) and cotton canvas (second substrate) was measured, and the initial adhesion was evaluated according to the following criteria. The results are shown in Table 3.
○: Peel strength is 45 N / inch or more ×: Peel strength is less than 45 N / inch
＜試験例２：最終接着性の評価＞
　積層体を、その製造後に室温で２４時間放置してから、剥離速度５０ｍｍ／分、剥離角度１８０度および室温の条件下で引張り試験機（島津製作所社製、オートグラフ）を用いて、積層体におけるＥＶＡ（第１の基材）と綿帆布（第２の基材）との剥離強度を測定し、以下の基準で最終接着性を評価した。結果を表３に示す。
　○：剥離強度が９０Ｎ／ｉｎｃｈ以上または材料破壊
　×：剥離強度が９０Ｎ／ｉｎｃｈ未満 <Test Example 2: Evaluation of final adhesion>
The laminate is allowed to stand at room temperature for 24 hours after the production, and then the laminate is used with a tensile tester (manufactured by Shimadzu Corporation, Autograph) under the conditions of a peeling rate of 50 mm / min, a peeling angle of 180 degrees, and room temperature. The peel strength between EVA (first substrate) and cotton canvas (second substrate) was measured, and the final adhesion was evaluated according to the following criteria. The results are shown in Table 3.
○: Peel strength is 90 N / inch or more or material destruction ×: Peel strength is less than 90 N / inch
　実施例８～１４および比較例６～１０で製造した積層体の種類；使用した水系接着剤の種類およびその後方散乱光強度の変化量の評価結果；並びに初期接着性および最終接着性の評価結果を、下記表３に示す。 Types of laminates produced in Examples 8 to 14 and Comparative Examples 6 to 10; results of evaluation of types of water-based adhesive used and the amount of change in backscattered light intensity; and results of evaluation of initial adhesiveness and final adhesiveness Is shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の後方散乱光強度の変化量の要件を満たす水系接着剤Ｆ１～Ｆ７を用いて製造した積層体１～７は、本発明の後方散乱光強度の変化量の要件を満たさない水系接着剤Ｆ８～Ｆ１２を用いて製造した積層体８～１２に比べて、初期接着性および最終接着性が良好であった。 The laminates 1 to 7 manufactured using the water-based adhesives F1 to F7 that satisfy the requirements for the amount of change in the backscattered light intensity of the present invention are the water-based adhesives that do not satisfy the requirements for the amount of change in the backscattered light intensity of the present invention. Compared with the laminates 8 to 12 produced using F8 to F12, the initial adhesiveness and final adhesiveness were good.
　本発明の分散液は、水系接着剤、プライマーまたはそれらの原料等として有用である。 The dispersion of the present invention is useful as an aqueous adhesive, a primer, or a raw material thereof.
　本願は、日本で出願された特願２０１６－２１２０８８号を基礎としており、その内容は本願明細書に全て包含される。 This application is based on Japanese Patent Application No. 2016-212088 filed in Japan, the contents of which are incorporated in full herein.

Claims (18)

  1. 　分散媒として水を含み、分散質として塩素化ゴムおよび重合性基を有する化合物を含む分散液であって、
    　塩素化ゴムおよび重合性基を有する化合物の合計量が、塩素化ゴム、重合性基を有する化合物および水の合計中に１～６０重量％であり、
    　３０ｍＬの分散液を１００ｍＬ容器に注ぎ、自転公転撹拌機を用いて、自転速度８００ｒｐｍおよび公転速度２，０００ｒｐｍの条件で１分間撹拌して測定試料を調製し、２０ｍＬの測定試料を直径２５ｍｍのシリンダー状の試料セルに注ぎ、試料セル中の測定試料に波長が８８０ｎｍである入射光を照射し、入射光に対して４５°の位置で測定試料からの後方散乱光を検出することによる後方散乱光強度（％）の測定を、測定試料の調製から１０分以内に開始し、試料セル中の測定試料の上部、中間部および底部のそれぞれにおける、測定を開始してから３０分後に測定した後方散乱光強度（％）に対する、測定を開始してから２４時間後に測定した後方散乱光強度（％）の変化量の絶対値における最大値α（％）が、下記式（I）～（III）：
    α（上部）　＜２０　　　（I）
    α（中間部）＜５　　　　（II）
    α（底部）　＜１０　　　（III）
    ［式中、α（上部）は、測定試料の上部における前記最大値α（％）を示し、α（中間部）は、測定試料の中間部における前記最大値α（％）を示し、α（底部）は、測定試料の底部における前記最大値α（％）を示し、測定試料の上部、中間部および底部は、それぞれ、メニスカスの部分を除いた試料セル中の測定試料の高さを上から１／３ずつ分割した測定試料の部分を示す。］
    の要件を満たす分散液。     A dispersion containing water as a dispersion medium and containing a compound having a chlorinated rubber and a polymerizable group as a dispersoid,
    The total amount of the chlorinated rubber and the compound having a polymerizable group is 1 to 60% by weight in the total amount of the chlorinated rubber, the compound having a polymerizable group and water,
    30 mL of the dispersion liquid is poured into a 100 mL container, and a measurement sample is prepared by stirring for 1 minute at a rotation speed of 800 rpm and a rotation speed of 2,000 rpm using a rotation and revolution stirrer. Back-scattered light by pouring into a sample cell, irradiating the measurement sample in the sample cell with incident light having a wavelength of 880 nm, and detecting back-scattered light from the measurement sample at a position of 45 ° to the incident light The intensity (%) measurement was started within 10 minutes from the preparation of the measurement sample, and the backscattering was measured 30 minutes after the start of measurement at each of the top, middle and bottom of the measurement sample in the sample cell. The maximum value α (%) of the absolute value of the amount of change in the backscattered light intensity (%) measured 24 hours after the start of measurement with respect to the light intensity (%) is expressed by the following formulas (I) to (III)
    α (upper part) <20 (I)
    α (intermediate part) <5 (II)
    α (bottom) <10 (III)
    [Wherein, α (upper part) represents the maximum value α (%) at the upper part of the measurement sample, α (middle part) represents the maximum value α (%) at the intermediate part of the measurement sample, and α ( Bottom) shows the maximum value α (%) at the bottom of the measurement sample, and the top, middle, and bottom of the measurement sample show the height of the measurement sample in the sample cell excluding the meniscus portion from the top. The part of the measurement sample divided by 1/3 is shown. ]
    A dispersion that meets the requirements of
  2. 　塩素化ゴム中の塩素原子含有量が、４５重量％以上である請求項１に記載の分散液。 The dispersion according to claim 1, wherein the chlorine atom content in the chlorinated rubber is 45% by weight or more.
  3. 　塩素化ゴムの量が、塩素化ゴムおよび重合性基を有する化合物の合計１００重量部に対して、１～３０重量部である請求項１または２に記載の分散液。 The dispersion according to claim 1 or 2, wherein the amount of the chlorinated rubber is 1 to 30 parts by weight based on 100 parts by weight of the total of the chlorinated rubber and the compound having a polymerizable group.
  4. 　塩素化ゴムの少なくとも一部が、液状の分散質中に溶解している請求項１～３のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 3, wherein at least a part of the chlorinated rubber is dissolved in the liquid dispersoid.
  5. 　重合性基を有する化合物の少なくとも一部が、２３℃および大気圧下にて液状である請求項１～４のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 4, wherein at least a part of the compound having a polymerizable group is liquid at 23 ° C and atmospheric pressure.
  6. 　塩素化ゴムの少なくとも一部が、２３℃および大気圧下にて液状である重合性基を有する化合物中に溶解している請求項５に記載の分散液。 The dispersion according to claim 5, wherein at least a part of the chlorinated rubber is dissolved in a compound having a polymerizable group that is liquid at 23 ° C. and atmospheric pressure.
  7. 　分散質が、液状である請求項１～３のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 3, wherein the dispersoid is liquid.
  8. 　重合性基を有する化合物が、エチレン性不飽和結合を有する化合物である請求項１～７のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 7, wherein the compound having a polymerizable group is a compound having an ethylenically unsaturated bond.
  9. 　さらに界面活性剤を含む請求項１～８のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 8, further comprising a surfactant.
  10. 　さらに光重合開始剤を含む請求項１～９のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 9, further comprising a photopolymerization initiator.
  11. 　さらに蛍光増白剤を含む請求項１～１０のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 10, further comprising a fluorescent brightening agent.
  12. 　さらにレベリング剤を含む請求項１～１１のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 11, further comprising a leveling agent.
  13. 　分散液中の分散質の体積基準のメジアン径が、１０μｍ以下である請求項１～１２のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 12, wherein the volume-based median diameter of the dispersoid in the dispersion is 10 µm or less.
  14. 　塩素化ゴムが、カルボキシ基およびカルボン酸無水物構造を有さない塩素化ゴムである請求項１～１３のいずれか一項に記載の分散液。 The dispersion according to any one of claims 1 to 13, wherein the chlorinated rubber is a chlorinated rubber having no carboxy group and no carboxylic anhydride structure.
  15. 　請求項１～１４のいずれか一項に記載の分散液から形成される塗膜。 A coating film formed from the dispersion according to any one of claims 1 to 14.
  16. 　請求項１５に記載の塗膜の硬化物。 A cured product of the coating film according to claim 15.
  17. 　第１の基材と、請求項１６に記載の硬化物と、接着剤層と、第２の基材とが、この順に積層されている積層体。 The laminated body by which the 1st base material, the hardened | cured material of Claim 16, an adhesive bond layer, and the 2nd base material are laminated | stacked in this order.
  18. 　第１の基材が、オレフィン系重合体またはエチレン－酢酸ビニル共重合体からなる請求項１７に記載の積層体。 The laminate according to claim 17, wherein the first base material comprises an olefin polymer or an ethylene-vinyl acetate copolymer.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0559188A (en) * 1991-08-29 1993-03-09 Dainippon Ink & Chem Inc Method for producing aqueous dispersion of chlorinated polyolefin resin
JPH0892524A (en) * 1994-09-19 1996-04-09 Nippon Shokubai Co Ltd Aqueous composite resin dispersion and its production
JP2007091997A (en) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc One pot type aqueous coating agent, method for producing the same and coated article
WO2015194611A1 (en) * 2014-06-20 2015-12-23 住友化学株式会社 Aqueous emulsion, coating film, cured product, and laminate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0559188A (en) * 1991-08-29 1993-03-09 Dainippon Ink & Chem Inc Method for producing aqueous dispersion of chlorinated polyolefin resin
JPH0892524A (en) * 1994-09-19 1996-04-09 Nippon Shokubai Co Ltd Aqueous composite resin dispersion and its production
JP2007091997A (en) * 2005-09-30 2007-04-12 Dainippon Ink & Chem Inc One pot type aqueous coating agent, method for producing the same and coated article
WO2015194611A1 (en) * 2014-06-20 2015-12-23 住友化学株式会社 Aqueous emulsion, coating film, cured product, and laminate

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